Triarylmethane compounds

ABSTRACT

The present invention relates to triarylmethane compounds of the formula (I), which suitable as monomers for preparing thermoplastic resins having beneficial optical properties and which can be used for producing optical devices. R 1 , R 2  are e.g. hydrogen; Y is an alkylene group having 2, 3 or 4 carbon atoms, Ar is selected from mono- or polycyclic aryl and mono- or polycyclic hetaryl; X 1 , X 2 , X 3 , X 4  are CH, C—R x  or N, provided that in each ring at most two of X 1 , X 2 , X 3 , X 4  are N; R x  is e.g. halogen, CN or CH═CH 2 . The invention also relates to thermoplastic resins comprising a polymerized unit of the compound of formula (I).

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to European Application No. 18156161.4,filed on Feb. 9, 2018.

The present invention relates to triarylmethane compounds that aresuitable as monomers for preparing thermoplastic resins, such aspolycarbonate resins, which have beneficial optical properties and canbe used for producing optical devices.

BACKGROUND OF INVENTION

Optical glass or optical resins are frequently used as a material for anoptical lens in optical systems of any of various types of cameras suchas a camera, a camera having a film integrated therewith, a video cameraand the like. While optical glass is beneficial in heat resistance,transparency, size stability, chemical resistance and the like, itsmaterial costs are high. Moreover the moldability is low and thus massproduction is difficult.

Optical devices, such as optical lenses, made of optical resin insteadof optical glass are advantageous in that they can be produced in largenumbers by injection molding. Nowadays, optical resins, in particular,transparent polycarbonate resins, are frequently used for producingcamera lenses. In this regard, resins with a higher refractive index arehighly desirable, as they allow for reducing the size and weight offinal products. In general, when using an optical material with a higherrefractive index, a lens element of the same refractive power can beachieved with a surface having less curvature, so that the amount ofaberration generated on this surface can be reduced. As a result, it ispossible to reduce the number of lenses, to reduce the eccentricsensitivity of lenses and/or to reduce the lens thickness to therebyachieve weight reduction.

In an optical system of a camera, the aberration correction is usuallyperformed by a combination of a plurality of concave and convex lenses.More specifically, a convex lens having a color aberration is combinedwith a concave lens having a color aberration of an opposite sign tothat of the convex lens, so that the color aberration of the convex lensis synthetically cancelled. In this case it is required that the concavelens is highly dispersive, i.e. it must have a low Abbe number.

EP2034337 describes a copolycarbonate resin which comprises 99 to 51 mol% of a repeating unit derived from9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 1 to 49 mol % of arepeating unit derived from bisphenol A. The resin is suitable forpreparing an optical lens having a low Abbe number of 23 to 26 and arefractive index from 1.62 to 1.64.

JP H06-25398 discloses a copolycarbonate resin including a repeatingunit derived from 9,9-bis(4-hydroxyphenyl)fluorene and a repeating unitderived from bisphenol A. In an example of this document, it isdescribed that the refractive index reaches 1.616 to 1.636.

U.S. Pat. No. 9,360,593 describes polycarbonate resins having repeatingunits derived from binaphthyl monomers of the formula (A):

where Y is C₁-C₄-alkandiyl, in particular 1,2-ethandiyl. It is said thatthe polycarbonate resins have beneficial optical properties in terms ofa high refractive index, a low Abbe's number, a high degree oftransparency, low birefringence, and a glass transition temperaturesuitable for injection molding.

Co-Polycarbonates of monomers of the formula A with10,10-bis(4-hydroxyphenyl)-anthrone monomers and their use for preparingoptical lenses are described in US 2016/0319069. The copolycarbonatesare reported to have a good moisture resistance. Refractive indices ofabout 1.662 to 1.667 have been reported. However, the thermoplasticprocessability, such as moldability, of the resins is poor.

So far, thermoplastic resin, such as a polycarbonate resins having ahigh refractive index and a low Abbe number and good thermoplasticprocessability have not been provided yet. Moreover, various electronicdevices should have high moisture resistance and heat resistance. A “PCTtest” (pressure cooker test) has been established to evaluate themoisture resistance and the heat resistance of such electronic devices.In this test, penetration of moisture into a sample is increased for acertain time period to evaluate the moisture resistance and the heatresistance. Therefore, an optical lens formed of an optical resinuseable for an electronic device needs to have a high refractive indexand a low Abbe number, and is also required to maintain high opticalproperties even after the PCT test.

Despite the advances made in the field of optical resins, here is stillan ongoing need for monomers for preparing optical resins, in particularpolycarbonate resins, which monomers result in a high refractive index.Apart from that, the monomers should not impair the other opticalproperties of the optical resins, and should provide at least one of thefollowing properties, namely low Abbe's number, a high degree oftransparency and low birefringence. Moreover, the monomers should beeasy to prepare. The resins obtained from these monomers should havealso a good moisture and heat resistance and they should have a glasstransition temperature suitable for injection molding. In particular,they should have a good thermoplastic processability, such asmoldability.

SUMMARY OF INVENTION

It was surprisingly found that compounds of the formula (I) as describedherein are suitable for preparing optical resins of high transparencyand high refractive index. In particular, when used as monomers in thepreparation of optical resins, compounds of the formula (I) result inhigher refractive indices than the monomers of formula (A).

Therefore, the present invention relates to compounds of the formula (I)

where

-   R¹, R² are hydrogen, a radical R^(a) or R¹ and R² together with the    carbon atoms to which they are bound may also form a fused benzene    ring, which is unsubstituted or substituted by one radical R^(a),-   Y represents an alkylene group having 2, 3 or 4 carbon atoms,-   Ar is selected from the group consisting of mono- or polycyclic aryl    having from 6 to 26 carbon atoms and mono- or polycyclic hetaryl    having a total of 5 to 26 atoms, which are ring members, where 1, 2,    3 or 4 of these atoms are selected from nitrogen, sulphur and    oxygen, while the remainder of these atoms are carbon atoms, where    mono- or polycyclic aryl and mono- or polycyclic hetaryl are    unsubstituted or carry 1, 23 or 4 radicals R^(Ar);-   X¹, X², X³, X⁴ are CH, C—R^(x) or N, provided that in each ring at    most two of X¹, X², X³, X⁴ are N;-   R^(a) is selected from the group consisting of fluorine,    cyclopropyl, cyclobutyl, CN, R, OR, CH_(n)R_(3-n), NR₂, C(O)R,    C(O)NH₂, CH═CH₂, CH═CHR, CH₂—CH═CH₂, CH₂—CH═CHR′, CH₂—C≡CH and    CH₂—C≡CR′;-   R^(Ar) is selected from the group consisting of fluorine,    cyclopropyl, cyclobutyl, CN, R, OR, CH_(n)R_(3-n), NR₂, C(O)R,    C(O)NH₂, CH═CH₂, CH═CHR′, CH₂—CH═CH₂, CH₂—CH═CHR′, CH₂—C≡CH and    CH₂—C≡CR′, it being possible that R^(Ar) is identical or different    if more than 1 is present on each ring;-   R^(x) is selected from the group consisting of halogen, cyclopropyl,    cyclobutyl, CN, R, OR, CH_(n)R_(3-n), NR₂, C(O)R, CH═CH₂, CH═CHR′,    CH₂—CH═CH₂, CH₂—CH═CHR′, CH₂—C≡CH and CH₂—C≡CR′, it being possible    that R^(x) is identical or different if more than 1 is present on    each ring;-   R is selected from methyl, mono or polycyclic aryl having from 6 to    26 carbon atoms and mono- or polycyclic hetaryl having a total of 5    to 26 atoms, which are ring members, where 1, 2, 3 or 4 of the ring    atoms of hetaryl are selected from nitrogen and oxygen, while the    remainder of these atoms are carbon atoms, where mono- or polycyclic    aryl are unsubstituted or substituted by 1, 2, 3 or 4 identical or    different radicals R″;-   R′ is selected from methyl, mono- or polycyclic aryl having from 6    to 26 carbon atoms and mono- or polycyclic hetaryl having a total of    5 to 26 atoms, which are ring members, where 1, 2, 3 or 4 of the    ring atoms of hetaryl are selected from nitrogen and oxygen, while    the remainder of these atoms are carbon atoms, where mono- or    polycyclic aryl are unsubstituted or substituted by 1, 2, 3 or 4    identical or different radicals R″;-   R″ is selected from fluorine, cyclopropyl, cyclobutyl, phenyl, CN,    OCH₃, CH₃, N(CH₃)₂, C(O)CH₃, CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂,    CH₂—CH═CH—CH₃, CH₂—C≡CH and CH₂—C≡C—CH₃;-   n on each occurrence is 0, 1, 2 or 3.

The above compounds are particularly useful in the preparation ofthermoplastic resins, in particular for optical resins as definedherein, in particular for polycarbonate resins polyestercarbonate resinsor polyester resins, especially for polycarbonate resins.

When used as monomers for the preparation of optical resins, inparticular polycarbonate resins, the compounds of the formula (I)provide for higher refractive indices of the resins than the monomers ofthe formula (A). Moreover, compounds of formula (I) provide for hightransparency of the resins and they do not significantly impair otheroptical properties and the mechanical properties of the resins. Inparticular, these resins fulfil the other requirements of opticalresins, such as low Abbe's number, a high degree of transparency and lowbirefringence. Apart from that, the monomers of formula (I) can beeasily prepared and obtained in high yields and high purity. Inparticular, the compounds of formula (I) can be obtained in crystallineform, which allows for an efficient purification to the degree requiredin the preparation of optical resins. In particular, the compounds offormula (I) can be obtained in a purity which provides for low haze,which is in particular important for the use in the preparation ofoptical resins. Compounds of formula (I), which do not bearcolor-imparting radicals, such as some of the radicals Ar, R and R′, canalso be obtained in a purity, which provides for a low yellowness indexY.I., as determined in accordance with ASTM E313, which may also beimportant for the use in the preparation of optical resins.

The invention also relates to a thermoplastic resin comprising apolymerized unit of the compounds of formula (I), i.e. a thermoplasticresin comprising a structural unit represented by formula (II) below

where

-   # represents a connection point to a neighboring structural unit;-   and where R¹, R², Ar, X¹, X², X³, X⁴ and Y are as defined herein.

The invention further relates to a thermoplastic resin selected fromcopolycarbonate resins, copolyestercarbonate resins and copolyesterresins, where the thermoplastic resin in addition to the structuralunits of formula (II) also comprises other structural units, inparticular those of the formula (V),#—O—R^(z)-A³-R^(z)—O-#-  (V)where

-   # represents a connection point to a neighboring structural unit;-   A³ is a polycyclic radical bearing at least 2 benzene rings, wherein    the benzene rings may be connected by A′ and/or directly fused to    each other and/or fused by a non-benzene carbocycle, where A³ is    unsubstituted or substituted by 1, 2 or 3 radicals R^(aa), which are    selected from the group consisting of halogen, C₁-C₆-alkyl,    C₅-C₆-cycloalkyl and phenyl;-   A′ is selected from the group consisting of a single bond, O, C═O,    S, SO₂, CH₂, CH—Ar″, CHAr″₂, CH(CH₃), C(CH₃)₂ and a radical A″

-   -   where    -   Q′ represents a single bond, O, NH, C═O, CH₂ or CH═CH; and    -   R^(10a), R^(10b), independently of each other are selected from        the group consisting of hydrogen, fluorine, CN, R, OR,        CH_(k)R_(3-k), NR₂, C(O)R and C(O)NH₂;

-   Ar″ is selected from the group consisting of mono- or polycyclic    aryl having from 6 to 26 carbon atoms and mono- or polycyclic    hetaryl having a total of 5 to 26 atoms, which are ring members,    where 1, 2, 3 or 4 of these atoms are selected from nitrogen,    sulphur and oxygen, while the remainder of these atoms are carbon    atoms, where Ar″ is unsubstituted or substituted by 1, 2 or 3    radicals R^(ab), which are selected from the group consisting of    halogen, phenyl and C₁-C₄-alkyl;

-   R^(z) is a single bond, Alk¹ or O-Alk²-, where O is bound to A³, and    where

-   Alk¹ is C₂-C₄-alkandiyl; and

-   Alk² is C₂-C₄-alkandiyl.

The invention further relates to an optical device made of athermoplastic resin as defined above.

The invention further relates to the se of the compound of formula (I)as defined herein as a monomer in the production of the thermoplasticresin as defined herein, in particular as a monomer in the production ofa copolycarbonate resin, a copolyestercarbonate resins or a copolyesterresin as defined herein.

DETAILED DESCRIPTION OF INVENTION

The compounds of formula (I) may have axial chirality due to the limitedrotation along the bonds between the carbon atom to which the moiety Aris attached and the two bicyclic units and therefore compounds of theformula (I) may exist in the form of a diastereomeric mixture of thethree configurational isomers, as a mixture of the two enantiomers, orin the form of one of the pure diastereomers, i.e. one of the twoenantiomers or of the meso form. The present invention relates to thediastereomeric mixture, the enantiomeric mixture as well as to the purediastereomers of the compounds of formula (I).

In terms of the present invention, the term “alkylene group having 1, 2,3 or 4 carbon atoms” is alternatively also designated “C₁-C₄-alkandiylgroup” and refers to a bivalent, saturated, aliphatic hydrocarbonradical having 1, 2, 3 or 4 carbon atoms. Examples of C₁-C₄-alkandiylare in particular linear alkandiyl such as methandiyl (═CH₂),1,2-ethandiyl (═CH₂CH₂), 1,3-propandiyl (═CH₂CH₂CH₂) and 1,4-butdandiyl(═CH₂CH₂CH₂CH₂), but also branched alkandiyl such as1-methyl-1,2-ethandiyl, 1-methyl-1,2-propandiyl,2-methyl-1,2-propandiyl, 2-methylpropandiyl and 1,3-butandiyl.

In terms of the present invention, the term “monocyclic aryl” refers tophenyl.

In terms of the present invention, the term “polycyclic aryl” refers to

(i) an aromatic polycyclic hydrocarbon radical, i.e. a completelyunsaturated polycyclic hydrocarbon radical, where each of the carbonatoms is part of a conjugate π-electron system,

(ii) a polycyclic hydrocarbon radical which bears 1 phenyl ring which isfused to a saturated or unsaturated 4 to 10-membered mono- or bicyclichydrocarbon ring,

(iii) a polycyclic hydrocarbon radical which bears at least 2 phenylrings which are linked to each other by a covalent bond or which arefused to each other directly and/or which are fused to a saturated orunsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring.

Usually, polycyclic aryl has from 9 to 26, e.g. 9, 10, 12, 13, 14, 16,17, 18, 19, 20, 22, 24, 25 or 26 carbon atoms, in particular from 10 to20 carbon atoms, especially 10, 12, 13, 14 or 16 carbon atoms.

In this context, polycyclic aryl bearing 2, 3 or 4 phenyl rings whichare linked to each other via a single bond include e.g. biphenylyl andterphenylyl. Polycyclic aryl bearing 2, 3 or 4 phenyl rings which aredirectly fused to each other include e.g. naphthyl, anthracenyl,phenanthrenyl, pyrenyl and triphenylenyl. Polycyclic aryl bearing 2, 3or 4 phenyl rings which are fused to a saturated or unsaturated 4- to10-membered mono- or bicyclic hydrocarbon ring include e.g.9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthenyl(1,2-dihydroacenaphthylenyl), acenaphthylenyl,9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl,5,6,7,8-tetrahydrophenanthrenyl, cyclopent[fg]acenaphthylenyl,phenalenyl, fluoranthenyl, benzo[k]fluoranthenyl, perylenyl,9,10-dihydro-9,10[1′,2′]-benzenoanthracenyl, dibenzo[a,e][8]annulenyl,9,9′-spirobi[9H-fluoren]yl andspiro[1H-cyclobuta[de]naphthalene-1,9′-[9H]fluoren]yl.

Polycyclic aryl includes, by way of example naphthyl, 9H-fluorenyl,phenanthryl, anthracenyl, pyrenyl, acenaphthenyl, acenaphthylenyl,2,3-dihydro-1H-indenyl, 5,6,7,8-tetrahydro-naphthalenyl,cyclopent[fg]acenaphthylenyl, 2,3-dihydrophenalenyl,9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl,5,6,7,8-tetrahydrophenanthrenyl, fluoranthenyl, benzo[k]fluoranthenyl,biphenylenyl, triphenylenyl, tetraphenylenyl,1,2-dihydroacenaphthylenyl, dibenzo[a,e][8]annulenyl, perylenyl,biphenylyl, terphenylyl, naphthylenphenyl, phenanthrylphenyl,anthracenylphenyl, pyrenylphenyl, 9H-fluorenylphenyl,di(naphthylen)phenyl, naphthylenbiphenyl, tri(phenyl)phenyl,tetra(phenyl)phenyl, pentaphenyl(phenyl), phenylnaphthyl, binaphthyl,phenanthrylnaphthyl, pyrenylnaphthyl, phenylanthracenyl,biphenylanthracenyl, naphthalenylanthracenyl, phenanthrylanthracenyl,dibenzo[a,e][8]annulenyl, 9,10-dihydro-9,10[1′,2′]benzoanthracenyl,9,9′-spirobi-9H-fluorenyl andspiro[1H-cyclobuta[de]naphthalene-1,9′-[9H]fluoren]yl.

In terms of the present invention, the term “monocyclic hetaryl” refersto a heteroaromatic monocycle, where the ring member atoms are part of aconjugate π-electron system, where the heteroaromatic monocycle has 5 or6 ring atoms, which comprise 1, 2, 3 or 4 nitrogen atoms or 1 oxygenatom and 0, 1, 2 or 3 nitrogen atoms, or 1 sulphur atom and 0, 1, 2 or 3nitrogen atoms, where the remainder of the ring atoms are carbon atoms.Examples include furyl (=furanyl), pyrrolyl (=1H-pyrrolyl), thienyl(=thiophenyl), imidazolyl (=1H-imidazolyl), pyrazolyl (=1H-pyrazolyl),1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl,1,3,4-oxadiazolyl, pyridyl (=pyridinyl), pyrazinyl, pyridazinyl,pyrimidinyl and triazinyl.

In terms of the present invention, the term “polycyclic hetaryl” refersto heteroaromatic polycyclic radicals, which bear a monocyclic hetarylring as defined above and at least one, e.g. 1, 2, 3, 4 or 5, furtheraromatic rings selected from phenyl and heteroaromatic monocycles asdefined above, where the aromatic rings of polycyclic hetaryl are linkedto each other by a covalent bond and/or fused to each other directlyand/or fused to a saturated or unsaturated 4 to 10-membered mono- orbicyclic hydrocarbon ring. The term “polycyclic hetaryl” also refers toheteroaromatic polycyclic radicals, which bear at least one saturated orpartially unsaturated 5- or 6-membered heterocyclic ring bearing 1 or 2heteroatoms selected from oxygen, sulphur and nitrogen as ring atoms,such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridin, 4H-1,4-oxazin4H-1,4-thiazin or 1,4-dioxin, and at least one, e.g. 1, 2, 3, 4 or 5,further aromatic rings selected from phenyl and heteroaromaticmonocycles, where at least one of the further aromatic rings is directlyfused to the saturated or partially unsaturated 5- or 6-memberedheterocyclic radical and where the remainder of further aromatic ringsof polycyclic hetaryl are linked to each other by a covalent bond orfused to each other directly and/or fused to a saturated or unsaturated4 to 10-membered mono- or bicyclic hydrocarbon ring. Usually polycyclichetaryl has 9 to 26 ring atoms in particular 9 to 20 ring atoms, whichcomprise 1, 2, 3 or 4 atoms selected from nitrogen atoms and oxygenatoms, where the remainder of the ring atoms are carbon atoms.

Examples of polycyclic hetaryl include, but are not limited to,benzofuryl, benzothienyl, dibenzofuranyl (=dibenzo[b,d]furanyl),dibenzothienyl (=dibenzo[b,d]thienyl), naphthofuryl, furo[3,2-b]furanyl,furo[2,3-b]furanyl, furo[3,4-b]furanyl, oxanthrenyl, indolyl(=1H-indolyl), isoindolyl (=2H-isoindolyl), carbazolyl, indolizinyl,benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl,1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl,quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl,cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl,naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl,pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl,pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl,puryl, 9H-xanthenyl, 2H-chromenyl, phenanthridinyl, phenanthrolinyl,furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl,furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl,benzo[g]chromenyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl,benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

In terms of the present invention, the term “optical device” refers to adevice that is transparent for visible light and manipulates lightbeams, in particular by refraction. Optical devices include but are notlimited to prisms, lenses, optical films and combinations thereof,especially lenses, e.g. lenses for cameras and lenses for glasses, andoptical films.

The remarks made below as to preferred embodiments of the variables(substituents) of the compounds of formula (I) and of the structuralunits of formula (II) are valid on their own as well as preferably incombination with each other, as well as in combination with thestereoisomers thereof.

The remarks made below concerning preferred embodiments of the variablesfurther are valid on their own as well as preferably in combination witheach other concerning the compounds of formula (I) and the structuralunits of formula (II), where applicable, as well as concerning the usesand methods according to the invention and the composition according tothe invention.

In formula (I) and likewise in formula (II), the variables Y, R¹, R²,Ar, X¹, X², X³ and X⁴ on their own or preferably in any combinationpreferably have the following meanings:

The variables Y in formulae (I) and (II) are in particular linearalkylene groups having 2, 3 or 4 carbon atoms, such as e.g.1,2-ethandiyl (CH₂—CH₂), 1,3-propandiyl or 1,4-butandiyl. Especially,the variables Y are 1,2-ethandiyl.

According to a first group (1) of embodiments, the radicals R¹ and R²are selected independently of one another from hydrogen and a radicalR^(a). Preferably, both radicals R¹ and R² are hydrogen. However, it mayalso be preferred that either R¹ or R² is a radical R^(a). In thiscontext, the radical R^(a) is preferably selected from the groupconsisting of fluorine, cyclopropyl, cyclobutyl, CN, OCH₃, CH₃, N(CH₃)₂,C(O)CH₃, CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂, CH₂—CH═CH—CH₃, CH₂—C≡CH andCH₂—C≡C—CH₃. In particular, R^(a), if present, is selected from thegroup consisting of fluorine, CN, OCH₃, CH₃ and CH═CH₂, especially fromthe group consisting of fluorine, CH═CH₂ and CN, and particularly fromCH═CH₂ and CN.

According to a second group (2) of embodiments, R¹ and R² together withthe carbon atoms to which they are bound form a fused benzene ring,which is unsubstituted or substituted by one radical R^(a), where R^(a)has one of the meanings defined herein, in particular one of thepreferred meanings. In this second group of embodiments it is preferredthat R¹ and R² together with the carbon atoms to which they are boundform a fused benzene ring, which is unsubstituted.

Especially, the radicals R¹ and R² are both hydrogen.

It is preferred that the basic structure of the radical Ar, i.e. themono/polycyclic aryl or mono/polycyclic hetaryl group, is unsubstitutedor bears 1, 2 or 3, in particular 1 or 2 and especially 1 radicalR^(Ar). Each radical R^(Ar) is typically bound to a carbon atom in anyposition of the basic structure of the radical Ar. For example, if thebasic structure of Ar is phenyl or 1-naphthyl the radicals R^(Ar) may beattached in position 2, 3 or 4 and in position 2, 3, 4, 5, 6, 7 or 8,respectively.

In a particular group (3) of embodiments of the present invention theradical Ar is selected from the group consisting of mono- and polycyclicaryl having a total of 6 to 26 atoms, in particular a total of 6 to 20carbon atoms, where mono- and polycyclic aryl are unsubstituted or carry1, 2, 3 or 4 radicals R^(Ar), with R^(Ar) having one of the meaningsdefined herein, in particular one of the preferred meanings.

In the group (3) of embodiments, the mono- or polycyclic aryl moietiessuitable as radical Ar are in particular selected from the groupconsisting of:

phenyl, naphthyl, phenanthryl, biphenylyl, 2,3-dihydro-1H-indenyl,1H-indenyl, 5,6,7,8-tetrahydronaphthalenyl, 1,2-dihydroacenaphthylenyl,acenaphthylenyl, 9,10-dihydroanthracen-1-yl,1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl,fluorenyl, anthracenyl, pyrenyl, biphenylenyl, triphenylenyl,tetraphenylenyl, 5H-dibenzo[a,d][7]annulenyl, perylenyl,9,9′-spirobi[9H-fluoren]yl and10,11-dihydro-5H-dibenzo[a,d][7]annulenyl, dibenzo[a,e][8]annulenyl,where mono- or polycyclic aryl is unsubstituted or substituted by 1radical R^(Ar).

In the group (3) of embodiments, the radical Ar in formulae (I) and (II)is more preferably a mono- or polycyclic aryl selected from the groupconsisting of phenyl, naphthyl, specifically 1- or 2-naphthyl,phenanthryl, specifically 9-phenanthryl, 1,2-dihydroacenaphthylenyl,specifically 1,2-dihydroacenaphthylen-5-yl, anthracenyl, specifically9-anthracenyl, 9H-fluorenyl, specifically 9H-fluoren-2-yl, pyrenylspecifically 3-pyrenyl, and biphenylyl, specifically 3- or 4-biphenylyl,which may be unsubstituted or substituted by 1 radical R^(Ar), withR^(Ar) having one of the meanings defined herein, in particular one ofthe preferred meanings.

In the group (3) of embodiments, the radical Ar in formulae (I) and (II)is especially a mono- or polycyclic aryl selected from the groupconsisting of phenyl, naphthyl, specifically 1- or 2-naphthyl,phenanthryl, specifically 9-phenanthryl, 1,2-dihydroacenaphthylenyl,specifically 1,2-dihydroacenaphthylen-5-yl, 9H-fluorenyl, specifically9H-fluoren-2-yl, biphenylenyl and biphenylyl, specifically 3- or4-biphenylyl, which may be unsubstituted or substituted by 1 radicalR^(Ar), with R^(Ar) having one of the meanings defined herein, inparticular one of the preferred meanings.

In the group (3) of embodiments, the radical Ar in formulae (I) and (II)is in particular a mono- or polycyclic aryl selected from the groupconsisting of phenyl, naphthyl, specifically 1- or 2-naphthyl,phenanthryl, specifically 9-phenanthryl, 1,2-dihydroacenaphthylenyl,specifically 1,2-dihydroacenaphthylen-5-yl, biphenylenyl and biphenylyl,specifically 3- or 4-biphenylyl, which may be unsubstituted orsubstituted by 1 radical R^(Ar), with R^(Ar) having one of the meaningsdefined herein, in particular one of the preferred meanings.

In another particular group (4) of embodiments of the present inventionthe radical Ar in formulae (I) and (II) is selected from the groupconsisting of mono- or polycyclic hetaryl having a total of 5 to 26atoms, which are ring members, where 1, 2, 3 or 4 of these atoms areselected from nitrogen, sulphur and oxygen, while the remainder of theseatoms are carbon atoms, where mono- or polycyclic hetaryl areunsubstituted or carry 1, 2, 3 or 4 radicals R^(Ar), with R^(Ar) havingone of the meanings defined herein, in particular one of the preferredmeanings.

Examples of such radicals include but are not limited to:

furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl,1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl,isothiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl,pyridazinyl, pyrimidinyl, triazinyl, benzofuryl, dibenzofuranyl,benzothienyl, dibenzothienyl, naphthofuryl, furo[3,2-b]furanyl,furo[2,3-b]furanyl, furo[3,4-b]furanyl, oxanthrenyl, indolyl,isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl,benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, 3H-benzo[e]indolyl,1H-benzo[f]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl,quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl,benzo[b][1,8]naphthyridin-3-yl, cinnolinyl,

1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl,naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl,pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[2,3-g]quinolinyl,pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl,pyrrolo[3,2-b]pyridinyl, pteridinyl, puryl, 9H-xanthenyl, 2H-chromenyl,4H-chromenyl, phenanthridinyl, phenanthrolinyl,furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl,furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl,2H-benzo[g]chromenyl, 4H-benzo[g]chromenyl, 3H-benzo[f]chromenyl,1-benzo[f]chromenyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl,benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

In the group (4) of embodiments, the radical Ar in formulae (I) and (II)is preferably a mono- or polycyclic hetaryl selected from the groupconsisting of furyl, benzofuryl, benzothienyl, naphthofuryl,dibenzofuranyl, dibenzothienyl, 9H-xanthenyl, 2H-chromenyl,4H-chromenyl, 2H-benzo[g]chromenyl, 4H-benzo[g]chromenyl,3H-benzo[f]chromenyl, 1H-benzo[f]chromenyl, furo[3,2-b]furanyl,furo[2,3-b]furanyl, furo[3,4-b]furanyl, 2,3-dihydro-1,4-benzodioxinyl,oxanthrenyl, furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl,pyrrolyl, indolyl, isoindolyl, carbazolyl, indolizinyl,benzo[cd]indolyl, 1H-benzo[g]indolyl, 3H-benzo[e]indolyl,1H-benzo[f]indolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl,phenanthridinyl, benzo[f]isoquinolinyl, benzo[h]isoquinolinyl,imidazolyl, pyrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl,benzopyrazolyl, benzimidazolyl, quinazolinyl, quinoxalinyl, cinnolinyl,1,5-naphthyridinyl, 1,8-naphthyridinyl, dipyridyl, pyrido[4,3-b]indolyl,pyrido[3,2-b]indolyl, pyrrolo[3,2-b]pyridinyl, phenazinyl,benzo[b][1,5]naphthyridinyl, phenanthrolinyl,benzo[b][1,8]naphthyridin-3-yl, pyrido[2,3-g]quinolinyl,pyrido[3,2-g]quinolinyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl,1,2,3-triazolyl, 1,2,4-triazolyl, triazinyl,pyrido[2,3-b][1,8]naphthyridinyl, tetrazolyl, oxazolyl, isoxazolyl,1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, benzoxazolyl, phenoxazinyl,furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl andfuro[2,3-g]quinoxalinyl, where mono- or polycyclic hetaryl isunsubstituted or substituted by 1 radical R^(Ar), with R^(Ar) having oneof the meanings defined herein, in particular one of the preferredmeanings.

In the group (4) of embodiments, the radical Ar in formulae (I) and (II)is in particular a mono- or polycyclic hetaryl selected from the groupconsisting of dibenzo[b,d]furanyl, specifically 2-, 3 or4-dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, specifically 2-, 3- or4-dibenzo[b,d]thienyl, pyrrolyl, specifically 2- or 3-pyrrolyl, indolyl,specifically 3-indolyl, pyridyl, specifically 2-, 3- or 4-pyridyl,quinolinyl, specifically 2-, 3- or 4-quinolinyl, isoquinolinyl,specifically 1- or 4-isoquinolinyl, and pyrimidinyl, specifically5-pyrimidinyl, which may be unsubstituted or substituted by 1 radicalR^(Ar), with R^(Ar) having one of the meanings defined herein, inparticular one of the preferred meanings.

In the context of the radical Ar, the radicals R^(Ar), if present, arepreferably independently selected from the group consisting of fluorine,cyclopropyl, cyclobutyl, CN, R, OR, CH_(n)R_(3-n), NR₂, C(O)R, C(O)NH₂,CH═CH₂, CH═CHR′, CH₂—CH═CH₂, CH₂—CH═CHR′, CH₂—C≡CH and CH₂—C≡CR′, wherethe variables R and R′ have the meanings defined herein, in particularthe preferred meanings.

Preferably, the radicals R^(Ar), if present, are independently selectedfrom the group consisting of fluorine, cyclopropyl, cyclobutyl, CN, CH₃,OCH₃, phenyl, naphthyl, anthracenyl, phenanthryl, 9H-fluorenyl,biphenylyl, dibenzo[b,d]furanyl, pyrrolyl, indolyl, pyridyl, quinolinyl,isoquinolinyl, pyrimidinyl, phenoxy, naphthyloxy, N(CH₃)₂, C(O)CH₃,CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂, CH₂—CH═CH—CH₃, CH₂—C≡CH, CH₂—C≡C—CH₃. Inthis context, R′ is preferably selected from the group consisting ofmethyl, phenyl, naphthyl, phenanthryl, biphenylyl, dibenzo[b,d]furanyl,pyrrolyl, indolyl, pyridyl, quinolinyl, isoquinolinyl and pyrimidinyl.

More preferably, the radicals R^(Ar), if present, are selected from thegroup consisting of fluorine, cyclopropyl, cyclobutyl, CN, CH₃, OCH₃,phenyl, phenoxy, naphthyloxy, N(CH₃)₂, C(O)CH₃, CH═CH₂, CH═CHCH₃,CH₂—CH═CH₂, CH₂—CH═CH—CH₃, CH₂—C≡CH and CH₂—C≡C—CH₃, especially from CN,CH₃, OCH₃, CH═CH₂ and phenyl, and in particular from CN, CH═CH₂ andphenyl.

In particular, the radicals R^(Ar), if present, are selected from thegroup consisting of CN, CH₃, OCH₃, phenyl and phenoxy, especially fromthe group consisting of CN and phenoxy.

In particular the radical Ar is selected from the group consisting ofradicals of the formulae Ar-1 to Ar-18;

where * indicates the point of attachment to the remainder of themolecule of the formula (I).

Particular examples of radicals Ar of the formulae Ar-1 to Ar-19 arephenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-phenylphenyl(=4-biphenylyl), 3-phenylphenyl (=3-biphenylyl), 4-phenoxylphenyl,9H-fluoren-2-yl, 1,2-dihydroacenaphthylen-5-yl, dibenzofuran-2-yl,dibenzofuran-3-yl, dibenzofuran-1-yl, dibenzofuran-4-yl,dibenzothien-2-yl, dibenzothien-3-yl, dibenzothien-1-yl,dibenzothien-4-yl, 4-quinolinyl, 2-quinolinyl, 3-quinolinyl,5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 1-isoquinolinyl,4-isoquinolinyl, 3-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl,7-isoquinolinyl, 8-isoquinolinyl, 1H-indol-3-yl, 1H-pyrrol-2-yl,1H-pyrrol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-pyrimidinyl,2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 4-cyano-1-naphthyl,5-cyano-1-naphthyl, 3-cyano-1-naphthyl, 6-cyano-1-naphthyl,4-cyano-2-naphthyl, 6-cyano-2-naphthyl, 5-cyano-2-naphthyl,7-cyano-2-naphthyl, 8-cyano-2-naphthyl, 2-cyano-9-phenanthryl,3-cyano-9-phenanthryl, 4-cyano-9-phenanthryl, 5-cyano-9-phenanthryl,6-cyano-9-phenanthryl and 7-cyano-9-phenanthryl.

Particularly preferred radicals Ar of the formulae Ar-1 to Ar-19 areselected from the group consisting of phenyl, 1-naphthyl, 2-naphthyl,9-phenanthryl, 4-phenylphenyl (=4-biphenylyl), 3-phenylphenyl(=3-biphenylyl), 4-phenoxylphenyl, 9H-fluoren-2-yl,1,2-dihydroacenaphthylen-5-yl, dibenzofuran-2-yl, dibenzofuran-3-yl,dibenzofuran-4-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl,dibenzo[b,d]thien-4-yl, 4-quinolinyl, 2-quinolinyl, 3-quinolinyl,1-isoquinolinyl, 4-isoquinolinyl, 1H-indol-3-yl, 1H-pyrrol-2-yl,1H-pyrrol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-pyrimidinyl,2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 4-cyano-1-naphthyl,5-cyano-1-naphthyl, 4-cyano-2-naphthyl and 6-cyano-2-naphthyl.

Preference is given to those compounds of formula (I) and likewise tothose units of formula (II), where either all of the variables X¹, X²,X³, X⁴ are CH or C—R^(x) or where in each ring at most one of X¹, X², X³and X⁴ is N, while the others are selected from CH and C—R^(x).

In a particular group (5) of embodiments of the present invention thevariables X¹, X², X³ and X⁴ are CH or C—R^(x), where the radical R^(x)has one of the meanings defined herein, in particular one of thepreferred meanings. Preferably, either all variables X¹, X², X³ or X⁴are CH or one of the variables X¹, X², X³ and X⁴ is C—R^(x) and thethree remaining variables are CH. In particular, the variables X¹ and X⁴are both CH, while one of X² and X³ is CH while the other is CH orC—R^(x).

In another particular group (6) of embodiments of the present inventionone of the four variables X¹, X², X³ or X⁴ is N and the three remainingvariables are CH or C—R^(x) and in particular are all three CH, wherethe radical R^(x) has one of the meanings defined herein, in particularone of the preferred meanings.

A skilled person will readily appreciate that the meanings of R¹ and R²of group (1) of embodiments may be combined with the meanings of Ar ofone of group (3) or group (4) of embodiments and also with the meaningsof X¹, X², X³ or X⁴ of one of group (5) or group (6) of embodiments. Askilled person will also appreciate that the meanings of R¹ and R² ofgroup (2) of embodiments may be combined with the meanings of Ar of oneof group (3) or group (4) of embodiments and also with the meanings ofX¹, X², X³ or X⁴ of one of group (5) or group (6) of embodiments.

Apart from that and if not stated otherwise, the radicals, R^(a), R^(x),R, R′ and R″ either alone or preferably in combination have thefollowing meanings.

R^(a) is in particular selected from the group consisting of fluorine,cyclopropyl, cyclobutyl, CN, CH₃, OCH₃, phenyl, naphthyl, anthracenyl,phenanthryl, biphenylyl, dibenzo[b,d]furanyl, pyrrolyl, indolyl,pyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, phenoxy, naphthyloxy,N(CH₃)₂, C(O)CH₃, CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂, CH₂—CH═CH—CH₃, CH₂—C≡CHand CH₂—C≡C—CH₃. More preferably, the radical R^(a) is selected from thegroup consisting of fluorine, cyclopropyl, cyclobutyl, CN, CH₃, OCH₃,phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, phenoxy,naphthyloxy, N(CH₃)₂, C(O)CH₃, CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂,CH₂—CH═CH—CH₃, CH₂—C≡CH and CH₂—C≡C—CH₃. In particular, the radicalR^(a) is selected from the group consisting of fluorine, cyclopropyl,CN, OCH₃, CH═CH₂, phenyl and phenoxy, more particular from CN, CH═CH₂and phenyl, and especially is CN.

Preferably, the radical R^(x) is selected from the group consisting ofbromine, fluorine, cyclopropyl, cyclobutyl, CN, CH₃, OCH₃, phenyl,naphthyl, anthracenyl, phenanthryl, biphenylyl, dibenzo[b,d]furanyl,pyrrolyl, indolyl, pyridyl, quinolinyl, isoquinolinyl, pyrimidinyl,phenoxy, naphthyloxy, N(CH₃)₂, C(O)CH₃, CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂,CH₂—CH═CH—CH₃, CH₂—C≡CH and CH₂—C≡C—CH₃. More preferably, the radicalR^(x) is selected from the group consisting of bromine, CN, CH₃, OCH₃,phenyl, naphthyl, anthracenyl, phenanthryl, pyridyl, phenoxy,naphthyloxy, N(CH₃)₂, C(O)CH₃, CH═CH₂, CH₂—C≡CH and CH₂—C≡C—CH₃. Inparticular, the radical R^(x) is selected from the group consisting ofbromine, CN, OCH₃, CH═CH₂, phenyl, naphthyl, phenanthryl and phenoxy,more particular from bromine, CN, CH═CH₂ and phenyl, and especially frombromine, CN and phenyl.

Preferably, the mono- or polycyclic aryl moieties suitable as radicals Rand R′ are selected from the group consisting of phenyl, naphthyl,phenanthryl, biphenylyl, dibenzo[b,d]furanyl, pyrrolyl, indolyl,pyridyl, quinolinyl, isoquinolinyl and pyrimidinyl. In particular, theradicals R or R′ are selected from the group consisting of phenyl,naphthyl, specifically 1- or 2-naphthyl and phenanthryl, specifically9-phenanthryl.

Preferably, the one or more radicals R″ are independently selected fromfluorine, phenyl, CN, OCH₃, CH₃, CH═CH₂ and CH═CHCH₃, in particular fromfluorine, phenyl and CN.

In a particular group (7) of preferred embodiments of the presentinvention the compound of the formula (I) and likewise the structuralunit of formula (II) bear at least one radical R^(Ar), R^(x), R¹ or R²which is selected from CN, CH═CH₂, phenyl or phenoxy, and in particularis CN.

A skilled person will readily appreciate that the particular group (7)of embodiments may be combined with the meanings of R¹ and R² of one ofgroup (1) or group (2) of embodiments, with the meanings of Ar of one ofgroup (3) or group (4) of embodiments and also with the meanings of X¹,X², X³ or X⁴ of one of group (5) or group (6) of embodiments.

In the group (7) of embodiments of the present invention a particularsubgroup (7a) of embodiments relates to the compounds of the formula (I)and the structural units of formula (II), which bear at least oneradical R^(Ar) or R^(x) which is CN or CH═CH₂, and especially is CN.

In yet a further group (8) of embodiments of the present invention thecompound of the formula (I) and likewise the structural unit of formula(II) do not bear any radical R^(Ar) or R^(x).

A skilled person will readily appreciate that the particular group (8)of embodiments may be combined with the meanings of R¹ and R² of one ofgroup (1) or group (2) of embodiments, with the meanings of Ar of one ofgroup (3) or group (4) of embodiments and also with the meanings of X¹,X², X³ or X⁴ of one of group (5) or group (6) of embodiments.

In a particular subgroup (1a) of groups (1) and (5) of embodiments thecompound of the formula (I) is a compound of the formula (Ia):

where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, the variable q is 0 or 1 and,if q is 1, the radicals R^(x) are located in in 6,6′ or 7,7′ positionsof the naphthyl ring, with R^(x) having one of the meanings definedherein, in particular one of the preferred meanings.

In this subgroup (1a) of groups (1) and (5) of embodiments thestructural unit of the formula (II) is a structural unit of the formula(IIa):

where # represents a connection point to a neighboring structural unitand where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, the variable q is 0 or 1 and,if q is 1, the radicals R^(x) are located in in 6,6′ or 7,7′ positionsof the naphthyl ring, with R^(x) having one of the meanings definedherein, in particular one of the preferred meanings.

In a particular subgroup (1a.1) of group (1a) of embodiments thevariable q in formulae (Ia) and (IIa) is 0.

In another particular subgroup (1a.2) of embodiments the variable q informulae (Ia) and (IIa), respectively, is 1. In this subgroup (1a.2),the radical R^(x) is preferably selected from the group consisting ofbromine, CN, phenyl, naphthyl, phenanthryl, biphenylyl,dibenzo[b,d]furanyl, pyrrolyl, indolyl, pyridyl, quinolinyl,isoquinolinyl and pyrimidinyl. In this particular subgroup (1a.2) ofembodiments the radical R^(x) is in particular selected from bromine,CN, phenyl, naphthyl and pyridyl. In this particular subgroup (1a.2) ofembodiments the radical R^(x) is particularly selected from bromine, CN,phenyl and naphthyl, and more particularly from bromine, CN and phenyl.

In a particular subgroup (2a) of groups (2) and (5) of embodiments ofthe invention the compound of the formula (I) is a compound of theformula (Ib):

where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, the variable q is 0 or 1, thevariable p is 0 or 1 and, if q is 1, the radicals R^(x) are located inin 6,6′ or 7,7′ positions of the phenanthryl ring, with R^(x) and R^(a)having the meanings defined herein, in particular the preferred ones.

In this subgroup (2a) of groups (2) and (5) of embodiments thestructural unit of the formula (II) is a structural unit of the formula(IIb):

where # represents a connection point to a neighboring structural unitand where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, the variable q is 0 or 1, thevariable p is 0 or 1 and, if q is 1, the radicals R^(x) are located inin 6,6′ or 7,7′ positions of the phenanthryl ring, with R^(x) and R^(a)having the meanings defined herein, in particular the preferred ones.

In a particular subgroup (2a.1) of subgroup (2a) of embodiments thevariables q and p in formulae (Ib) and (IIb), respectively, are both 0.

In another particular subgroup (2a.2) of subgroup (2a) of embodimentsthe variable q in formulae (Ib) and (IIb), respectively, is 1 and thevariable p in formulae (Ib) and (IIb), is 0.

In a further particular subgroup (2a.3) of subgroup (2a) of embodimentsthe variable q in formulae (Ib) and (IIb), respectively, is 0 and the pin formulae (Ib) and (IIb), respectively, is 1.

In yet a further particular subgroup (2a.4) of subgroup (2a) ofembodiments the variables q and p in formulae (Ib) and (IIb),respectively, are both 1.

In case the variable q in formulae (Ib) and (IIb), respectively, is 1,the radical R^(x) is preferably selected from the group consisting ofbromine, CN, phenyl, naphthyl, phenanthryl, biphenylyl,dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, pyrrolyl, indolyl, pyridyl,quinolinyl, isoquinolinyl and pyrimidinyl. In this context the radicalR^(x) is preferably selected from the group consisting of bromine, CN,phenyl, naphthyl and pyridyl. In this context the radical R^(x) is inparticular selected from the group consisting of bromine, CN, phenyl,and naphthyl, and more particularly from bromine, CN and phenyl.

In case the variable p in formulae (Ib) and (IIb), respectively, is 1,the radical R^(a) is preferably selected from the group consisting offluorine, CN, CH₃, OCH₃, phenyl, naphthyl, anthracenyl, phenanthryl,biphenylyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, pyrrolyl, indolyl,pyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, phenoxy, naphthyloxy,N(CH₃)₂, C(O)CH₃, CH═CH₂, CH₂—C≡CH and CH₂—C≡C—CH₃. In this context theradical R^(a) is more preferably selected from fluorine, CN, CH₃, OCH₃,phenyl, naphthyl and pyridyl. In this context the radical R^(a) is inparticular selected from CN, phenyl and naphthyl, and more particularlyfrom CN and phenyl.

In another particular subgroup (1 b) of groups (1) and (6) ofembodiments the compound of the formula (I) is a compound of one offormulae (Ic), (Id), (Ie) or (If):

where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, and the variables Y are asdefined herein and preferably are linear alkylene groups having 2, 3 or4 carbon atoms, in particular 1,2-ethandiyl.

In this subgroup (1b) of groups (1) and (6) of embodiments thestructural unit of the formula (II) is a structural unit of the formulae(IIc), (IId), (IIe) or (IIf):

where # represents a connection point to a neighboring structural unitand where the radical Ar has one of the meanings defined herein, inparticular one of the preferred meanings, and the variables Y are asdefined herein and preferably are linear alkylene groups having 2, 3 or4 carbon atoms, in particular 1,2-ethandiyl.

In a particular subgroup (1c) of groups (1) and (5) of embodiments thecompound of formula (I) is a compound of formula (Ia′), where R^(x1) andR^(x2) are hydrogen or have one of the meanings, in particular thepreferred meanings given for R^(x) as defined herein and Ar is asdefined herein and has in particular one of the preferred meanings.

Examples of the compounds of the particular subgroup (1c) are thecompounds of formula (Ia′), where the combination of Ar, R^(x1) andR^(x2) as defined in one row of table A below. In the following table A,also the refractive indices no of several compounds of the formula (Ia′)at wavelength of 589 nm are summarized. The refractive indices of thecompounds of formula (Ia′) were calculated by using the computersoftware ACD/ChemSketch 2012 (Advanced Chemistry Development, Inc.).

TABLE A # R^(x1) R^(x2) Ar n_(D) (calc.) 1 H H phenyl 1.67 2 H H1-naphthyl 1.70 3 H H 2-naphthyl 1.70 4 H H 9-phenanthryl 1.73 5 H H4-phenylphenyl 1.67 6 H H 3-phenylphenyl 1.67 7 H H 4-phenoxyphenyl 1.668 H H 9H-fluoren-2-yl 1.70 9 H H 1,2-dihydroacenaphthylen-5-yl 1.72 10 HH dibenzofuran-2-yl 1.72 11 H H dibenzofuran-4-yl 1.72 12 H Hdibenzothien-2-yl 1.74 13 H H dibenzothien-4-yl 1.74 14 H H 4-quinolinyl1.71 15 H H 2-quinolinyl 1.71 16 H H 3-quinolinyl 1.71 17 H H1-isoquinolinyl 1.71 18 H H 4-isoquinolinyl 1.71 19 H H 1H-indol-3-yl1.72 20 H H 1H-pyrrol-2-yl 1.69 21 H H 1H-pyrrol-3-yl 1.69 22 H H2-pyridyl 1.68 23 H H 3-pyridyl 1.68 24 H H 4-pyridyl 1.68 25 H H5-pyrimidinyl 1.68 26 H H 2-cyanophenyl 1.71 27 H H 3-cyanophenyl 1.7128 H H 4-cyanophenyl 1.71 29 H H 4-cyano-1-naphthyl 1.74 30 H H5-cyano-1-naphthyl 1.74 31 H H 4-cyano-2-naphthyl 1.74 32 H H6-cyano-2-naphthyl 1.74 33 Br H phenyl 1.69 34 Br H 1-naphthyl 1.72 35Br H 2-naphthyl 1.72 36 Br H 9-phenanthryl 1.74 37 Br H 4-phenylphenyl1.69 38 Br H 3-phenylphenyl 1.69 39 Br H 4-phenoxyphenyl 1.69 40 Br H9H-fluoren-2-yl 1.72 41 Br H 1,2-dihydroacenaphthylen-5-yl 1.73 42 Br Hdibenzofuran-2-yl 1.74 43 Br H dibenzofuran-4-yl 1.74 44 Br Hdibenzothien-2-yl 1.75 45 Br H dibenzothien-4-yl 1.75 46 Br H4-quinolinyl 1.72 47 Br H 2-quinolinyl 1.72 48 Br H 3-quinolinyl 1.72 49Br H 1-isoquinolinyl 1.72 50 Br H 4-isoquinolinyl 1.72 51 Br H1H-indol-3-yl 1.73 52 Br H 1H-pyrrol-2-yl 1.71 53 Br H 1H-pyrrol-3-yl1.71 54 Br H 2-pyridyl 1.70 55 Br H 3-pyridyl 1.70 56 Br H 4-pyridyl1.70 57 Br H 5-pyrimidinyl 1.70 58 Br H 2-cyanophenyl 1.74 59 Br H3-cyanophenyl 1.74 60 Br H 4-cyanophenyl 1.74 61 Br H 4-cyano-1-naphthyl1.77 62 Br H 5-cyano-1-naphthyl 1.77 63 Br H 4-cyano-2-naphthyl 1.77 64Br H 6-cyano-2-naphthyl 1.77 65 CN H phenyl 1.72 66 CN H 1-naphthyl 1.7467 CN H 2-naphthyl 1.74 68 CN H 9-phenanthryl 1.77 69 CN H4-phenylphenyl 1.73 70 CN H 3-phenylphenyl 1.73 71 CN H 4-phenoxyphenyl1.72 72 CN H 9H-fluoren-2-yl 1.75 73 CN H 1,2-dihydroacenaphthylen-5-yl1.76 74 CN H dibenzofuran-2-yl 1.77 75 CN H dibenzofuran-4-yl 1.77 76 CNH dibenzothien-2-yl 1.78 77 CN H dibenzothien-4-yl 1.78 78 CN H4-quinolinyl 1.75 79 CN H 2-quinolinyl 1.75 80 CN H 3-quinolinyl 1.75 81CN H 1-isoquinolinyl 1.75 82 CN H 4-isoquinolinyl 1.75 83 CN H1H-indol-3-yl 1.76 84 CN H 1H-pyrrol-2-yl 1.73 85 CN H 1H-pyrrol-3-yl1.73 86 CN H 2-pyridyl 1.72 87 CN H 3-pyridyl 1.72 88 CN H 4-pyridyl1.72 89 CN H 5-pyrimidinyl 1.72 90 CN H 2-cyanophenyl 1.72 91 CN H3-cyanophenyl 1.72 92 CN H 4-cyanophenyl 1.72 93 CN H 4-cyano-1-naphthyl1.75 94 CN H 5-cyano-1-naphthyl 1.75 95 CN H 4-cyano-2-naphthyl 1.75 96CN H 6-cyano-2-naphthyl 1.75

In this subgroup (1c) of groups (1) and (5) of embodiments thestructural unit of the formula (II) is a structural unit of the formula(IIa′):

where # represents a connection point to a neighboring structural unitand where R^(x1) and R^(x2) are hydrogen or have one of the meanings, inparticular the preferred meanings given for R^(x) as defined herein andAr is as defined herein and has in particular one of the preferredmeanings. Examples of such structural units (IIa′) are those, where thecombination of Ar, R^(x1) and R^(x2) as defined in one row of table A.

The compounds of the formula (I) as well as precursors thereof can beprepared for example by the process depicted in the following reactionscheme 1, starting from the phenol derivative of the formula (VI) andthe aryl aldehyde of the formula (VII) (compare for example: J. P.Poupelin et al., Eur. J. Med. Chem. 1978, 13(1), 67-71; A. Alizadeh etal., J. Iran. Chem. Soc., 2010, 7(2), 351-358; and J. P. Poupelin etal., Eur. J. Med. Chem. 1978, 13(4), 381-71):

In scheme 1 the variables R¹, R², Ar, X¹, X², X³ and X⁴ are as definedherein.

In step i) of the process according to scheme 1, the phenol derivative(VI) and the aryl aldehyde (VII) undergo a condensation reaction in thepresence of an acid catalyst to yield the diol of the formula (VIII).Suitable acids for catalyzing the reaction of step i) are generallystrong acids, such as sulfuric acid, methanesulfonic acid andp-toluenesulfonic acid, in particular methanesulfonic acid. The reactionis typically carried out in a polar organic solvent such asC₂-C₆-alkanols, such as isopropanol, and halogenated C₁-C₄-alkanes, suchas dichloromethane, at a reaction temperature that is usually in therange of 0 to 60° C. and particularly in the range of 10 to 40° C.

In step ii) of scheme 1 the diol of formula (VIII) is reacted with acyclic carbonate of the formula (IX),

where Y is as defined above and in particular 1,2-ethandiyl, to yieldthe compound of formula (I). Hence, an example of a suitable compound offormula (IX) is ethylene carbonate. The compound of formula (IX) isusually applied in excess of the desired stoichiometry, i.e. the molarratio of compound (IX) to the diol (VIII) exceeds 2:1 and is inparticular in the range from 2.2:1 to 5:1. The reaction according tostep ii) of scheme 1 is usually performed in the presence of a base, inparticular an oxo base, especially an alkaline carbonate such as sodiumcarbonate or potassium carbonate. The base is usually used in catalyticamounts, e.g. in amount from 0.1 to 0.5 mol per 1 mol of the diol(VIII). Frequently, the reaction of the diol of formula (VIII) with thecompound of formula (IX) is performed in an aprotic organic solvent, inparticular in an aromatic hydrocarbon solvent such as toluene or xyleneand mixtures thereof. The reaction according to step ii) of scheme 1 isusually performed at temperatures in the range from 50 to 150° C.

In case the variables X¹, X², X³ and X⁴ of the compound of the formula(I) include substituents R^(x) that are bromine, a further step iii) maybe added to the reaction sequence of scheme 1 in order to replacebromine atoms with substituents R^(x) that are as defined above and areattached to the remainder of the molecule via an alkyl, alkenyl or a(het)aryl group. Examples of such substituents R^(x) are CH₃, CH═CH₂,phenyl, naphthyl or pyridyl. In step iii) the compound of formula (I) isreacted with an boronic compound of the formula (X),R^(x)—B(OH)₂  (X)where R^(x) is as defined above, provided that it is attached to theremainder of the molecule via an alkyl, alkenyl or a (het)aryl group,or, alternatively, reacted with an ester or anhydride of (X), inparticular a C₁-C₄-alkyl ester of (X), in the presence of a transitionmetal catalyst, in particular in the presence of a palladium catalyst.Frequently, step iii) is performed under the conditions of a so-called“Suzuki Reaction” or “Suzuki Coupling” (see e.g. A. Suzuki et al., Chem.Rev. 1995, 95, 2457-2483; N. Zhe et al., J. Med. Chem. 2005, 48 (5),1569-1609; Young et al., J. Med. Chem. 2004, 47 (6), 1547-1552; C. Sleeet al., Bioorg. Med. Chem. Lett. 2001, 9, 3243-3253; T. Zhang et al.,Tetrahedron Lett., 52 (2011), 311-313, S. Bourrain et al., Synlett. 5(2004), 795-798, B. Li et al., Europ. J. Org. Chem. 20113932-3937).Suitable transition metal catalysts are in particular palladiumcompounds, which bear at least one palladium atom and at least onetri-substituted phosphine ligand. Examples of palladium catalysts aretetrakis(triphenylphosphine) palladium, tetrakis(tritolylphosphine)palladium and[1,1-bis(diphenylphosphino)ferro-cene]dichloropalladium(II)(PdCl₂(dppf)). Frequently, the palladium catalysts are prepared in situfrom a suitable palladium precursor and a suitable phosphine ligand.Suitable palladium precursors are palladium compounds such astris-(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) or palladium(II)acetate (Pd(OAc)₂). Suitable phosphine ligands are in particulartri(substituted)phosphines, e.g. a triaryl-phosphines such astriphenylphosphine, tritolylphosphine or2,2′-bis(diphenyl-phosphino)-1,1′-binaphthalene (BINAP),tri(cyclo)alkylphosphine such as tris-n-butylphosphine,tris(tert-butyl)phosphine or tris(cyclohexylphosphine), ordicyclohexyl-(2′,4′,6′-tri-iso-propyl-biphenyl-2-yl)-phosphane (X-Phos).Usually, the reaction is performed in the presence of a base, inparticular an oxo base, such as an alkaline alkoxide, earth alkalinealkoxide, alkaline hydroxides, earth alkaline hydroxides, alkalinephosphates, earth alkaline phosphates, alkaline carbonates or earthalkaline carbonates such as or sodium ethoxide, sodium tert-butoxide,potassium tert-butoxide, lithium hydroxide, barium hydroxide, potassiumphosphate, sodium carbonate, potassium carbonate, or cesium carbonate.Frequently, the reaction according to step iii) is performed in anorganic solvent or in a mixture thereof with water. If the reaction isperformed in a mixture of an organic solvent and water, the reactionmixture may be monophasic or biphasic. Suitable organic solvents includebut are not limited to aromatic hydrocarbons such as toluene or xylene,acyclic and cyclic ethers, such as methyl tert.-butyl ether, ethyltert.-butyl ether, diisopropylether, dioxane or tetrahydrofurane,ketones, such as 2-butanone, and aliphatic alcohols having 1 to 4 carbonatoms, such as methanol, ethanol or isopropanol, as well as mixturesthereof. The reaction according to step iii) is usually performed attemperatures in the range from 50 to 150° C.

Rather than subsequent to step ii), the conversion according to stepiii) can alternatively be carried out after step i) and before step ii)of the reaction sequence depicted in scheme 1, i.e. instead of thesequence step i), step ii), step iii) the alternative sequence step i),step iii), step ii) is followed. It is also possible to start from abromine containing naphthol type compound of the formula (VI),subjecting this compound to the conversion according to step iii) andthen perform steps i) and ii) as outlined above.

If carried out in the alternative sequence step i), step iii), step ii),the reaction conditions for the individual reaction of steps i), ii) andiii) are the same or almost the same as described above for the sequencestep i), step ii), step iii).

The reaction mixtures obtained in the individual steps i) to iii) areworked up in a conventional way, e.g. by mixing with water, separatingthe phases and, where appropriate, purifying the crude products bywashing, chromatography or crystallization. The intermediates in somecases result in the form of colourless or pale brownish, viscous oils,which are freed of volatiles or purified under reduced pressure and atmoderately elevated temperature. If the intermediates are obtained assolids, the purification can be achieved by recrystallization or washingprocedures, such as slurry washing.

The compounds of the formulae (VI), (VII), (IX) and (X) are commerciallyavailable or can be prepared by methods known from the art.

As stated above, the compounds of the present invention can be obtainedin high purity, which means that a product is obtained, which does notcontain significant amounts of organic impurities different from thecompound of formula (I), except for volatiles. Usually, the purity ofcompounds of formula (I) is at least 95%, in particular at least 98% andespecially at least 99%, based on the non-volatile organic matter, i.e.the product contains at most 5%, in particular at most 2% and especiallyat most 1% of non-volatile impurities different from the compound offormula (I).

The term “volatiles” refers to organic compounds, which have a boilingpoint of less than 200° C. at standard pressure (105 Pa). Consequently,non-volatile organic matter is understood to mean compounds having aboiling point, which exceeds 200° C. at standard pressure.

It is a particular benefit of the invention that the compounds offormulae (I), (Ia), (Ia′), (Ib), (Ic), (Id), (Ie) and (If), and likewisetheir solvates, can often be obtained in crystalline form. In thecrystalline form the compound of formula (I) may be present in pure formor in the form of a solvate with water or an organic solvent. Therefore,a particular aspect of the invention relates to the compounds of formula(I), which are essentially present in crystalline form. In particular,the invention relates to crystalline forms, where the compound offormula (I) is present without solvent and to the crystalline solvatesof the compounds of formula (I), where the crystals contain a solventincorporated.

It is a particular benefit of the invention that the compounds of theformulae (I), (Ia), (Ia′), (Ib), (Ic), (Id), (Ie) and (If), and likewisetheir solvates, can often be easily crystallized from conventionalorganic solvents. This allows for an efficient purification of thecompounds of formula (I). Suitable organic solvents for crystallizingthe compounds of the formula (I) or their solvates, include but are notlimited to aromatic hydrocarbons such as toluene or xylene, aliphaticketones in particular ketones having from 3 to 6 carbon atoms, such asacetone, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone,aliphatic and alicyclic ethers, such as diethyl ester, dipropyl ether,methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether,dioxane or tetrahydrofurane, and aliphatic alcohols having 1 to 4 carbonatoms, such as methanol, ethanol or isopropanol, as well as mixturesthereof.

Alternatively, the compounds of the formulae (I), (Ia), (Ia′), (Ib),(Ic), (Id), (Ie) and (If), and likewise their solvates, can be obtainedin purified form by employing other simple and efficient methods forpurifying the raw products of the compounds of the formula (I), such asin particular slurry washing the raw solids obtained directly after theconversion to prepare the compounds of formula (I). Slurry washing istypically conducted at ambient temperature or elevated temperatures ofusually about 30 to 90° C., in particular 40 to 80° C. Suitable organicsolvents here are in principle the same as those listed above as beingsuitable for crystallizing the compounds of formula (I), such as inparticular the mentioned aromatic hydrocarbons, aliphatic ketones andaliphatic ethers, e.g. toluene, methyl ethyl ketone and methyltert-butyl ether.

Accordingly, the compounds of formulae (I), (Ia), (Ia′), (Ib), (Ic),(Id), (Ie) and (If), respectively, used for the preparation of thethermoplastic polymers, in particular the polycarbonates, as definedherein, can be easily prepared and obtained in high yield and highpurity. In particular, compounds of formulae (I), (Ia), (Ia′), (Ib),(Ic), (Id), (Ie) and (If), respectively, can be obtained in crystallineform, which allows for an efficient purification to the degree requiredin the preparation of optical resins. In particular, these compounds canbe obtained in a purity which provides for high refractive indices andalso low haze, which is particularly important for the use in thepreparation of optical resins of which the optical devise is made of. Inconclusion, the compounds of formulae (I), (Ia), (Ia′), (Ib), (Ic),(Id), (Ie) and (If), respectively, are particularly useful as monomersin the preparation of the optical resins.

A skilled person will readily appreciate that the formula (I) of themonomer used corresponds to the formula (II) of the structural unitcomprised in the thermoplastic resin. Likewise, the formulae (Ia),(Ia′), (Ib), (Ic), (Id), (Ie) and (If), respectively, of the monomerused corresponds to the formulae (IIa), (IIa′), (IIb), (IIc), (IId),(IIe) and (IIf), respectively, of the structural unit comprised in thethermoplastic resin.

A skilled person will also appreciate that the structural units of theformulae (II), (IIa), (IIa′), (IIb), (IIc), (IId), (IIe) and (IIf) arerepeating units within the polymer chains of the thermoplastic resin.

In addition to the structural units of the formulae (II), (Ia), (Ia′),(IIb), (IIc), (IId), (IIe) and (IIf), respectively, the thermoplasticresin may have structural units different therefrom. In a preferredembodiment, these further structural units are derived from aromaticmonomers of the formula (IV) resulting in structural units of theformula (V):HO—R^(z)-A³-R^(z)—OH  (IV)#—O—R^(z)-A³-R^(z)—O-#  (V)where

-   A³ is a polycyclic radical bearing at least 2 benzene rings, wherein    the benzene rings may be connected by A′ and/or directly fused to    each other and/or fused by a non-benzene carbocycle, where A³ is    unsubstituted or substituted by 1, 2 or 3 radicals R^(aa), which are    selected from the group consisting of halogen, C₁-C₆-alkyl,    C₅-C₆-cycloalkyl and phenyl, in particular phenyl and methyl;-   A′ is selected from the group consisting of a single bond, O, C═O,    S, SO₂, CH₂, CH—Ar″, CHAr″₂, CH(CH₃), C(CH₃)₂ and a radical A″

-   -   where    -   Q′ represents a single bond, O, NH, C═O, CH₂ or CH═CH, in        particular a single bond or C═O; and    -   R^(10a), R^(10b), independently of each other are selected from        the group consisting of hydrogen, fluorine, CN, R, OR,        CH_(k)R_(3-k), NR₂, C(O)R and C(O)NH₂ and where R^(10a), R^(10b)        are in particular hydrogen;

-   Ar″ is selected from the group consisting of mono- or polycyclic    aryl having from 6 to 26 carbon atoms and mono- or polycyclic    hetaryl having a total of 5 to 26 atoms, which are ring members,    where 1, 2, 3 or 4 of these atoms are selected from nitrogen,    sulphur and oxygen, while the remainder of these atoms are carbon    atoms, in particular phenyl or naphthyl, where Ar″ is unsubstituted    or substituted by 1, 2 or 3 radicals R^(ab), which are selected from    the group consisting of halogen, C₁-C₆-alkyl, C₅-C₆-cycloalkyl and    phenyl, in particular phenyl and methyl;

-   R^(z) is a single bond, Alk¹ or O-Alk²-, where O is bound to A³, and    where

-   Alk¹ is C₂-C₄-alkandiyl;

-   Alk² is C₂-C₄-alkandiyl, in particular linear alkandiyl having 2 to    4 carbon atoms and especially CH₂CH₂; and

-   # represents a connection point to a neighboring structural unit.

In the context of formulae (IV) and (V), A³ is in particular apolycyclic radical bearing 2 benzene or naphthaline rings, wherein thebenzene rings are connected by A′. In this context A′ is in particularselected from the group consisting of a single bond, CH—Ar″, CHAr″₂, anda radical A″.

In the context of formulae (IV) and (V), R^(z) is in particular O-Alk²-,where Alk² is in particular linear alkandiyl having 2 to 4 carbon atomsand especially CH₂CH₂

Amongst the monomers of formula (IV) preference is given to monomers ofthe general formulae (IV-1) to (IV-8), where R^(z) and R^(aa) are asdefined herein and R^(z) is in particular selected from a single bond,CH₂ and OCH₂CH₂:

Examples of compounds of the formulae—(IV-1) to (IV-8) are9,9-bis(4-hydroxyphenyl)fluorene,9,9-bis(4-hydroxy-3-methylphenyl)fluorene,9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene,9,9-bis(4-hydroxy-3-tert.-butylphenyl)fluorene,9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene,9,9-bis(4-hydroxy-3-phenylphenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-tert.-butylphenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene,9,9-bis(6-hydroxy-2-naphthyl)fluorene,9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene,10,10-bis(4-hydroxyphenyl)anthracen-9-on,10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-on,4,4′-dihydroxy-tetraphenylmethane,4,4′-di-(2-hydroxyethoxy)-tetraphenylmethane,3,3′-diphenyl-4,4′-dihydroxy-tetraphenylmethane,di-(6-hydroxy-2-naphthyl)-diphenylmethane,2,2′-[1,1′-binaphthalene-2,2′-diylbis(oxy)]diethanol also termed2,2′-bis(2-hydroxyethoxy)-1,1′-binaphtyl,2,2′-bis(1-hydroxyethoxy)-1,1′-binaphtyl,2,2′-bis(3-hydroxypropyloxy)-1,1′-binaphtyl,2,2′-bis(4-hydroxybutoxy)-1,1′-binaphtyl, and the like. Among themonomers of the general formula (IV) or of formulae (IV-1) to (IV-8),particular preference is given to the monomers of formulae (IV-1),(IV-2), (IV-3) and (IV-8) with particular preference given to2,2′-bis(2-hydroxyethoxy)-1,1′-binaphtyl,9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene and9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

Accordingly, amongst the structural units of formula (V) that may becomprised in the thermoplastic resin preference is given to monomers ofthe general formulae (V-1) to (V-8), where R^(z) is as defined hereinand is in particular selected from a single bond and OCH₂CH₂:

The monomers of formula (I) used for producing the thermoplastic resinmay contain certain impurities resulting from their preparation, e.g.hydroxy compounds, which bear an OH group instead of a group —O—Y—OH.The total amount of such hydroxy compounds is preferably 1000 ppm orlower, more preferably 500 ppm or lower, still more preferably 200 ppmor lower, and especially preferably 100 ppm or lower. The total contentof the impurities in the monomers used for preparing the thermoplasticresin is preferably 1000 ppm or lower.

Suitable thermoplastic resins for the preparation of optical devices,such as lenses and optical films, are in particular polycarbonates,polyestercarbonates and polyesters. Preferred thermoplastic resins forthe preparation of optical devices, such as lenses and optical films,are in particular polycarbonates.

Said polycarbonates are structurally characterized by having structuralunits of at least one of the formulae (II), (IIa), (IIa′), (IIb), (IIc),(IId), (IIe) and (IIf), respectively, optionally structural unitsderived from diol monomers, which are different from the monomercompound of the formula (I), e.g. structural units of the formula (V),#—O—R^(z)-A³-R^(z)—O-#  (V)

-   -   where    -   #, R^(z) and A³ are as defined herein above;        and a structural unit of formula (ill-1) stemming from the        carbonate forming component:

where each # represents a connection point to a neighboring structuralunit, i.e. to 0 at the connection point of the structural unit of theformula (II) and, if present, to 0 at the connection point of thestructural unit of the formula (V).

Said polyesters are structurally characterized by having structuralunits of at least one of the formulae (II), (IIa), (IIa′), (IIb), (IIc),(IId), (IIe) and (IIf), respectively, optionally structural unitsderived from diol monomers which are different from the monomer compoundof the formula (I), e.g. structural units of the formula (V), andstructural units derived from dicarboxylic acid, e.g. of formula (III-2)in case of a benzene dicarboxylic acid, of formula (III-3) in case of anaphthalene carboxylic acid, of formula (III-4) in case of oxalic acid,of formula (III-5) in case of malonic acid and of formula III-6 in caseof binaphthyl dicarboxylic acids, such as2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl:

In formulae (III-2) to (III-6) each variable # represents a connectionpoint to a neighboring structural unit, i.e. to O of the connectionpoint of the structural unit of the formula (II) and, if present, to Oof the connection point of the structural unit of the formula (V). Informula (III-6) the variable A^(v) may be a single bond, C₁-C₄-alkyleneor C₁-C₄-alkylene-O, such as CH₂O.

Said polyestercarbonates are structurally characterized by havingstructural units of at least one of the formulae (II), (IIa), (IIa′),(IIb), (IIc), (IId), (IIe) and (IIf), respectively, optionallystructural units derived from diol monomers which are different from themonomer compound of the formula (I), e.g. structural units of theformula (V), a structural unit of formula (III-1) stemming from thecarbonate forming component and structural units derived fromdicarboxylic acid, e.g. of formula (III-2) in case of a benzenedicarboxylic acid, of formula (III-3) in case of a naphthalenecarboxylic acid, of formula (III-4) in case of oxalic acid and offormula (III-5) in case of malonic acid.

A particular group of embodiments relates to thermoplastic copolymerresins, in particular polycarbonates, polyestercarbonates andpolyesters, which have both structural units of formula (II) and one ormore structural units of formula (V), i.e. resins, in particularpolycarbonates, polyestercarbonates and polyesters, which are obtainableby reacting at least one monomer of formula (I) with one or moremonomers of formula (IV). In this case the molar ratio of monomers offormula (I) to monomers of formula (IV) and likewise the molar ratio ofthe structural units of formula (II) to structural units of formula (V)are in the range from 5:95 to 80:20, in particular in the range from10:90 to 70:30 and especially in the range from 15:85 to 60:40.

The thermoplastic copolymer resins of the present invention, such as apolycarbonate resin may include either one of a random copolymerstructure, a block copolymer structure, and an alternating copolymerstructure. The thermoplastic resin according to the present inventiondoes not need to include all of structural units (II) and one or moredifferent structural units (V) in one, same polymer molecule. Namely,the thermoplastic copolymer resin according to the present invention maybe a blend resin as long as the above-described structures are eachincluded in any of a plurality of polymer molecules. For example, thethermoplastic resin including all of structural units (II) andstructural units (V) described above may be a copolymer including all ofstructural units (II) and structural units (V), it may be a mixture of ahomopolymer or a copolymer including at least one structural unit (II)and a homopolymer or a copolymer including at least one structural unit(V) or it may be a blend resin of a copolymer including at least onestructural unit (II) and a first structural unit (V) and a copolymerincluding at least one structural unit (II) and at least one otherstructural unit (V) different from the first structural units (V); etc.

Thermoplastic polycarbonates are obtainable by polycondensation of adiol component and a carbonate forming component. Similarly,thermoplastic polyesters and polyestercarbonates are obtainable bypolycondensation of a diol component and a dicarboxylic acid, or anester forming derivative thereof, and optionally a carbonate formingcomponent.

The thermoplastic resin composition which includes a polycarbonate resinmay contain, as impurities, phenol generated during the production ofthe polycarbonate resin, or carbonate diester or a material monomerremaining without being reacted. The concentration of the phenol in thethermoplastic resin composition is will generally not exceed 3000 ppm,in particular 2000 ppm and especially 1000 ppm and is frequently in therange from 0.1 to 3000 ppm, in particular 0.1 to 2000 ppm, and stillmore preferably 0.1 to 1000 ppm, 0.1 to 800 ppm, 0.1 to 500 ppm or 0.1to 300 ppm. The concentration of the carbonate diester in thethermoplastic resin composition will generally not exceed 1000 ppm, inparticular 500 ppm and especially 100 ppm and is frequently in the rangefrom 0.1 to 1000 ppm, in particular 0.1 to 500 ppm, and especially 0.1to 100 ppm. The concentration of the material monomer, i.e. monomers ofthe formula (I) and optionally (V) in the thermoplastic resincomposition will generally not exceed 3000 ppm, in particular 2000 ppmand especially 1000 ppm and is frequently in the range from 0.1 to 3000ppm, more preferably 0.1 to 2000 ppm, and especially preferably 1 to1000 ppm.

The concentrations of the phenol and the carbonate diester in thethermoplastic resin composition may be adjusted to obtain a resin havingproperties suitable to the use thereof. The concentrations of thephenol, the carbonate diester, and the material monomer may beappropriately adjusted by changing the conditions or the device ofpolycondensation. Alternatively, the concentrations of the phenol andthe carbonate diester may be adjusted by changing the conditions in anextrusion step after the polycondensation.

In the case where the concentration of the phenol or the carbonatediester is higher than the above-described range, a problem may occurthat the strength of the resultant resin molded body is decreased orthat an odor is generated, for example. By contrast, in the case wherethe concentrations of the phenol, the carbonate diester, or the materialmonomer may serve for a certain plasticity. Consequently, when theirconcentration is lower than the above-described ranges, the plasticityof the resin when the resin is melted may but be but not necessarily isundesirably decreased.

The weight-average molecular weight (Mw), as determined by GPC describedbelow, of the thermoplastic resin according to the present invention ispreferably in the range from 5000 to 100000 Dalton, more preferably 7500to 80000 Dalton, and still more preferably 10000 to 70000 Dalton. Thenumber-average molecular weight (Mn) of the thermoplastic resinaccording to the present invention is preferably 2000 to 20000, morepreferably 2500 to 15000, and still more preferably 3000 to 14000.

The value of the molecular weight distribution (Mw/Mn) of thethermoplastic resin according to the present invention is preferably 1.0to 15.0, more preferably 1.5 to 12.0, and still more preferably 2.0 to9.5.

The above-mentioned polycarbonate resin has a high refractive index(n_(D) or n_(d)) and thus is suitable to an optical lens. The values ofthe refractive index as referred herein are values of a film having athickness of 0.1 mm may be measured by use of an Abbe refractive indexmeter by a method of JIS-K-7142. The refractive index of thepolycarbonate resin according to the present invention at 23° C. at awavelength of 589 nm is, in case the resin includes the structural unit(II), preferably 1.640 or higher, more preferably 1.650 or higher, stillmore preferably 1.660 or higher. For example, the refractive index ofthe copolycarbonate resin including the structural unit (II) and astructural unit (V) according to the present invention is preferably1.640 to 1.690, preferably 1.650 to 1.690, still more preferably 1.660to 1.690.

The Abbe number (v) of the polycarbonate resin is preferably 25 orlower, more preferably 23 or lower, and still more preferably 21 orlower. The Abbe number may be calculated by use of the followingequation based on the refractive index at wavelengths of 487 nm, 589 nmand 656 nm at 23° C.v=(n _(D)−1)/(n _(F) −n _(C))

-   -   n_(D): refractive index at a wavelength of 589 nm    -   n_(C): refractive index at a wavelength of 656 nm    -   n_(F): refractive index at a wavelength of 486 nm

The glass transition temperature (Tg) of the polycarbonate resin as anexample of the thermoplastic resin according to the present inventionis, in consideration of that the polycarbonate is usable for injectionmolding, preferably 95 to 190° C., more preferably 130 to 180° C., andstill more preferably 145 to 170° C. With regard to the molding fluidityand the molding heat resistance, the lower limit of Tg is preferably135° C. and more preferably 140° C., and the upper limit of Tg ispreferably 190° C. and more preferably 180° C. A glass transitiontemperature (Tg) in the above given ranges provides a significant rangeof usable temperature and avoids the risk that the melting temperatureof the resin may be too high, and thus the resin may be undesirablydecomposed or colored. What is more, it allows for preparing moldshaving a high surface accuracy.

An optical molded body such as an optical element produced by using apolycarbonate resin of the present invention has a total lighttransmittance of preferably 85% or higher, more preferably 87% orhigher, and especially preferably 88% or higher. A total lighttransmittance of preferably 85% or higher is as good as that provided bybisphenol A type polycarbonate resin or the like.

The thermoplastic resin according to the present invention has highmoisture and heat resistance. The moisture and heat resistance may beevaluated by performing a “PCT test” (pressure cooker test) on a moldedbody such as an optical element produced by use of the thermoplasticresin and then measuring the total light transmittance of the moldedbody after the PCT test. In the PCT test, first, an injection moldedbody having a diameter of 50 mm and a thickness of 3 mm is kept for 20hours with PC305S III made by HIRAYAMA Corporation under the conditionsof 120° C., 0.2 MPa, 100% RH for 20 hours. Then, the sample of theinjection molded body is removed from the device and the total lighttransmittance is measured using the SE2000 type spectroscopic parallaxmeasuring instrument made by Nippon Denshoku Industries Co., Ltd inaccordance with the method of JIS-K-7361-1.

The thermoplastic resin according to the present invention has apost-PCT test total light transmittance of 60% or higher, preferably 70%or higher, more preferably 75% or higher, still more preferably 80% orhigher, and especially preferably 85% or higher. As long as the totallight transmittance is 60% or higher, the thermoplastic resin isconsidered to have a higher moisture and heat resistance than that ofthe conventional thermoplastic resin.

The thermoplastic resin according to the present invention has a bvalue, which represents the hue, of preferably 5 or lower. As the bvalue is smaller, the color is less yellowish, which is good as a hue.

According to the invention, the diol component, which is used in thepreparation of the polycarbonates or polyesters, may additionallycomprise one or more diol monomers, which are different from the monomercompound of the formula (I), such as one or more monomers of the formula(IV).

Suitable diol monomers, which are different from the monomer compound ofthe formula (I), are those, which are conventionally used in thepreparation of polycarbonates, e.g.

-   -   aliphatic diols such as ethylene glycol, propanediol,        butanediol, pentanediol and hexanediol;    -   alicyclic diols such as tricyclo[5.2.1.02,6]decane dimethanol,        cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane        dimethanol, pentacyclopentadecane dimethanol,        cyclopentane-1,3-dimethanol, spiroglycol,        1,4:3,6-dianhydro-D-sorbitol, 1,4:3,6-dianhydro-D-mannitol and        1,4:3,6-dianhydro-L-iditol are also included in examples of the        diol; and    -   aromatic diols, in particular aromatic diols of the formula        (IV), such as bis(4-hydrophenyl)methane,        1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyhenyl)ether,        bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,        bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone,        2,2-bis(4-hydroxyphenyl)propane,        2,2-bis(4-hydroxy-3-t-butylphenyl)propane,        2,2-bis(4-hydroxy-3-methylphenyl)propane,        1,1-bis(4-hydroxyphenyl)cyclopentane,        1,1-bis(4-hydroxyphenyl)cyclohexane,        2,2-bis(4-hydroxyphenyl)hexafluoro-propane,        bis(4-hydroxyphenyl)diphenylmethane,        1,1-bis(4-hydroxyphenyl)-1-phenylethane,        α,ω-bis[2-(p-hydroxyphenyl)ethyl]polydimethylsiloxane,        α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane,        4,4′-[1,3-phenylenebis(1-methylethylidene)hydroxyphenyl]-1-phenylethane,        9,9-bis(4-hydroxyphenyl)fluorene,        9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene,        9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene,        9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene,        9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene,        9,9-bis(4-hydroxy-3-methylphenyl)fluorene,        9,9-bis(4-hydroxy-3-phenylphenyl)fluorene,        9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene,        9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene,        9,9-bis(6-hydroxy-2-naphthyl)fluorene,        9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene,        10,10-bis(4-hydroxyphenyl)anthracen-9-on,        10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-on and        2,2′-[1,1′-binaphthalene-2,2′-diylbis(oxy)]diethanol, also        termed 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthyl or        2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (BNE).

Preferably, the diol component comprises at least one monomer of theformula (IV) in addition to the monomer of formula (I). In particular,the total amount of monomers of formulae (I) and (IV) contribute to thediol component by at least 90% by weight, based on the total weight ofthe diol component or by at least 90 mol-%, based on the total molaramount of the diol monomers of the diol component. In particular, thediol component comprises at least one monomer selected from the monomersof formulae (IV-1) to (IV-8) in addition to the monomer of formula (I).More particularly, the diol component comprises at least one monomerselected from the monomers of formulae (IV-1), (IV-2), (IV-3) and (IV-8)in addition to the monomer of formula (I). Especially, the diolcomponent comprises at least one monomer selected from2,2′-bis(2-hydroxyethoxy)-1,1′-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphtyl,9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-fluorene and9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and combinationsthereof in addition to the monomer of formula (I).

Frequently, the relative amount of monomer compound of formula (I),based on the total weight of the diol component, is at least 5% byweight, in particular at least 10% by weight, especially at least 15% byweight, preferably in the range of 5 to 90% by weight, in particular inthe range of 10 to 80% by weight, especially in the range of 15 to 70%by weight, but may also be as high as 100% by weight.

Frequently, the relative molar amount of monomer compound of formula(I), based on the total molar of the diol component, is at least 5mol-%, in particular at least 10 mol-% and especially at least 15 mol-%,preferably in the range of 5 to 80 mol-%, in particular in the range of10 to 70 mol-%, especially in the range of 15 to 60 mol-%, but may alsobe as high as 100 mol-%.

Consequently, the relative molar amount of monomer compound of formula(IV), based on the total molar of the diol component, will typically notexceed 95 mol-%, in particular not exceed 90 mol-% and especially notexceed 85 mol-%, and is preferably in the range of 20 to 95 mol-%, inparticular in the range of 30 to 90 mol-%, especially in the range of 40to 85 mol-%, but may also be as high as 99.9 mol-%.

Frequently, the total molar amount of monomers of formula (I) andmonomers of formula (IV) is at least 80 mol-%, in particular at least 90mol-%, especially at least 95 mol-% or up to 100 mol-%, based on thetotal molar amount of the diol monomers in the diol component.

Examples of further preferred aromatic dihydroxy compounds, which can beused in addition to the monomers of formula (I) and optionally monomersof formula (IV) include, but are not limited to bisphenol A, bisphenolAP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E,bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P,bisphenol PH, bisphenol TMC, bisphenol Z and the like.

In order to adjust the molecular weight and the melt viscosity, themonomers forming the thermoplastic polymer may also include amonofunctional compound, in case of polycarbonates a monofunctionalalcohol and in case of polyesters a monofunctional alcohol or amonofunctional carboxylic acid. Suitable monoalcohols are butanol,hexanol and octanol. Suitable monocarboxylic acids include e.g. benzoicacid, propionic acid and butyric acid. In order to increase themolecular weight and the melt viscosity, the monomers forming thethermoplastic polymer may also include a polyfunctional compound, incase of polycarbonates a polyfunctional alcohol having three or morehydroxyl groups and in case of polyesters a polyfunctional alcoholhaving three or more hydroxyl groups or a polyfunctional carboxylic acidhaving three or more carboxyl groups. Suitable polyfunctional alcoholsare e.g. glycerine, trimethylol propane, pentaerythrit and1,3,5-trihydroxy pentane. Suitable polyfunctional carboxylic acidshaving three or more carboxyl groups are e.g. trimellitic acid andpyromellitic acid. The total amount of these compounds, will frequentlynot exceed 10 mol-%, based on the molar amount of the diol component.

Suitable carbonate forming monomers, are those, which are conventionallyused as carbonate forming monomers in the preparation of polycarbonates,include, but are not limited to phosgene, diphosgene and diestercarbonates such as diethyl carbonate, diphenyl carbonate, di-p-tolylcarbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate anddinaphthyl carbonate. Out of these, diphenyl carbonate is particularlypreferred. The carbonate forming monomer is frequently used at a ratioof 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, with respectto 1 mol of the dihydroxy compound(s) in total.

Suitable dicarboxylic acids include, but are not limited to

-   -   aliphatic dicarboxylic acids such as oxalic acid, malonic acid,        succinic acid, glutaric acid, adipic acid, pimelic acid, suberic        acid, azelaic acid;    -   alicyclic dicarboxylic acids such as tricyclo[5.2.1.02,6]decane        dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid,        decalin-2,6-dicarboxylic acid, and norbornandicarboxylic acid;        and    -   aromatic dicarboxylic acids, such as benzene dicarboxylic acids,        specifically phthalic acid, isophthalic acid,        2-methylterephthalic acid or terephthalic acid, and naphthalene        dicarboxylic acids, specifically naphthalene-1,3-dicarboxylic        acid, naphthalene-1,4-dicarboxylic acid,        naphthalene-1,5-dicarboxylic acid, naphthalene-1,6-dicarboxylic        acid, naphthalene-1,7-dicarboxylic acid,        naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic        acid, naphthalene-2,7-dicarboxylic acid and binaphthyl        dicarboxylic acids, such as        2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl.

Suitable ester forming derivatives of dicarboxylic acids include, butare not limited to the dialkyl esters, the diphenyl esters and theditolyl esters.

In case of polyesters, the ester forming monomer is frequently used at aratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, withrespect to 1 mol of the dihydroxy compound(s) in total.

The polycarbonates of the present invention can be prepared by reactinga diol component comprising a monomer of formula (I) and optionally afurther diol monomer such as a monomer of the formula (IV) and acarbonate forming monomer by analogy to the well known preparation ofpolycarbonates as described e.g. in U.S. Pat. No. 9,360,593, US2016/0319069 and US 2017/0276837, to which full reference is made.

The polyesters of the present invention can be prepared by reacting adiol component comprising a monomer of formula (I) and optionally afurther diol monomer such as a monomer of the formula (IV) and adicarboxylic acid or its ester forming derivative by analogy to the wellknown preparation of polyesters as described e.g. in US 2017/044311 andthe references cited therein, to which full reference is made.

The polyestercarbonates of the present invention can be prepared byreacting a diol component comprising a monomer of formula (I) andoptionally a further diol monomer such as a monomer of the formula (IV),a carbonate forming monomer and a dicarboxylic acid or its ester formingderivative by analogy to the well known preparation ofpolyestercarbonates as described in the art.

The polycarbonates, polyesters and polyestercarbonates are usuallyprepared by reacting the monomers of the diol component with thecarbonate forming monomers and/or the ester forming monomers, i.e. thedicarboxylic acids or the ester forming derivatives thereof, in thepresence of an esterification catalyst, in particular atransesterification catalyst, in case a carbonate forming monomer or anester forming derivative of a polycarboxylic acid is used.

Suitable transesterification catalysts are basic compounds, whichspecifically include but are not limited to alkaline metal compounds,alkaline earth metal compound, nitrogen-containing compounds, and thelike. Likewise, suitable transesterification catalysts are acidiccompounds, which specifically include but are not limited to Lewis acidcompounds of polyvalent metals, including compounds of as zinc, tin,titanium, zirconium, lead, and the like.

Examples of suitable alkaline metal compound include alkaline metalsalts of an organic acid such as acetic acid, stearic acid, benzoicacid, or phenylphorsphoric acid, alkaline metal phenolates, alkalinemetal oxides, alkaline metal carbonates, alkaline metal borohydrides,alkaline metal hydrogen carbonates, alkaline metal phosphate, alkalinemetal hydrogenphosphate, alkaline metal hydroxides, alkaline metalhydrides, alkaline metal alkoxides, and the like. Specific examplesthereof include sodium hydroxide, potassium hydroxide, cesium hydroxide,lithium hydroxide, sodium hydrogen carbonate, sodium carbonate,potassium carbonate, cesium carbonate, lithium carbonate, sodiumacetate, potassium acetate, cesium acetate, lithium acetate, sodiumstearate, potassium stearate, cesium stearate, lithium stearate, sodiumborohydride, sodium borophenoxide, sodium benzoate, potassium benzoate,cesium benzoate, lithium benzoate, disodium hydrogen phosphate,dipotassium hydrogen phosphate, dilithium hydrogen phosphate, anddisodium phenylphosphate; and also include disodium salt, dipotassiumsalt, dicesium salt, dilithium salt of bisphenol A, sodium salt,potassium salt, cesium salt and lithium salt of phenol; and the like.

Examples of the alkaline earth metal compound include alkaline earthmetal salts of an organic acid such as acetic acid, stearic acid,benzoic acid, or phenylphorsphoric acid, alkaline earth metalphenolates, alkaline earth metal earth oxides, alkaline earth metalcarbonates, alkaline metal borohydrides, alkaline earth metal hydrogencarbonates, alkaline earth metal hydroxides, alkaline earth metalhydrides, alkaline earth metal alkoxides, and the like. Specificexamples thereof include magnesium hydroxide, calcium hydroxide,strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate,calcium hydrogen carbonate, strontium hydrogen carbonate, bariumhydrogen carbonate, magnesium carbonate, calcium carbonate, strontiumcarbonate, barium carbonate, magnesium acetate, calcium acetate,strontium acetate, barium acetate, magnesium stearate, calcium stearate,calcium benzoate, magnesium phenylphosphate, and the like.

Examples of the nitrogen-containing compound include quaternaryammoniumhydroxide, salt thereof, amines, and the like. Specific examplesthereof include quaternary ammoniumhydroxides including an alkyl group,an aryl group or the like, such as tetramethylammoniumhydroxide,tetraethylammoniumhydroxide, tetrapropylammoniumhydroxide,tetrabutylammoniumhydroxide, trimethylbenzylammoniumhydroxide, and thelike; tertiary amines such as triphenylamine, dimethylbenzylamine,triphenylamine, and the like; secondary amines such as diethylamine,dibutylamine, and the like; primary amines such as propylamine,butylamine, and the like; imidazoles such as 2-methylimidazole,2-phenylimidazole, benzoimidazole, and the like; bases or basic saltssuch as ammonia, tetramethylammoniumborohydride,tetrabutylammoniumborohydride, tetrabutylammoniumtetraphenylborate,tetraphenylammoniumtetraphenylborate, and the like.

Preferred examples of the transesterification catalyst include salts ofpolyvalent metals such as zinc, tin, titanium, zirconium, lead, and thelike, in particular the chlorides, alkoxyides, alkanoates, benzoates,acetylacetonates and the like. They may be used independently or in acombination of two or more. Specific examples of suchtransesterification catalyst include zinc acetate, zinc benzoate, zinc2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate(II), tin acetate (IV), dibutyltinlaurate, dibutyltinoxide,dibutyltinmethoxide, zirconiumacetylacetonate, zirconium oxyacetate,zirconiumtetrabutoxide, lead acetate (II), lead acetate (IV), and thelike.

The transesterification catalyst are frequently used at a ratio of 10⁻⁹to 10⁻³ mol, preferably 10⁻⁷ to 10⁻⁴ mol, with respect to 1 mol of thedihydroxy compound(s) in total.

Frequently, the polycarbonates, polyesters and polyestercarbonates areprepared by a melt polycondensation method. In the melt polycondensationthe monomers are reacted in the absence of an additional inert solvent.While the reaction is performed any byproduct formed in thetransesterification reaction is removed by heating the reaction mixtureat ambient pressure or reduced pressure.

The melt polycondensation reaction preferably comprises charging themonomers and catalyst into a reactor and subjecting the reaction mixtureto conditions, where the reaction between the monomers and the formationof the byproduct takes place. It has been found advantages, if thebyproduct resides for at least a while in the polycondensation reaction.However, in order to drive the polycondensation reaction to the productside, it is beneficial to remove at least a portion of the formedbyproduct during or preferably at the end of the polycondensationreaction. In order to allow the byproduct in the reaction mixture, thepressure may be controlled by closing the reactor, or by increasing ordecreasing the pressure. The reaction time for this step is 20 minutesor longer and 240 minutes or shorter, preferably 40 minutes or longerand 180 minutes or shorter, and especially preferably 60 minutes orlonger and 150 minutes or shorter. In this step, in the case where thebyproduct is removed by distillation soon after being generated, thefinally obtained thermoplastic resin has a low content of highmolecular-weight resin molecules. By contrast, in the case where thebyproduct is allowed to reside in the reactor for a certain time, thefinally obtained thermoplastic resin has a high content of highmolecular-weight resin molecules.

The melt polycondensation reaction may be performed in a continuoussystem or in a batch system. The reactor usable for the reaction may beof a vertical type including an anchor-type stirring blade, a Maxblend®stirring blade, a helical ribbon-type stirring blade or the like; of ahorizontal type including a paddle blade, a lattice blade, an eyeglass-type blade or the like; or an extruder type including a screw. Areactor including a combination of such reactors is preferably usable inconsideration of the viscosity of the polymerization product.

According to the method for producing the thermoplastic resin, such as apolycarbonate resin, after the polymerization reaction is finished, thecatalyst may be removed or deactivated in order to maintain the thermalstability and the hydrolysis stability. A preferred method fordeactivating the catalyst is the addition of an acidic substance.Specific examples of the acidic substance include esters such as butylbenzoate and the like; aromatic sulfonates such as p-toluenesulfonicacid and the like; aromatic sulfonic acid esters such as butylp-toluenesulfonate, hexyl p-toluenesulfonate, and the like; phosphoricacids such as phosphorous acid, phosphoric acid, phosphonic acid, andthe like; phosphorous acid esters such as triphenyl phosphite,monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propylphosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctylphosphite, monooctyl phosphite, and the like; phosphoric acid esterssuch as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate,dibutyl phosphate, dioctyl phosphate, monooctyl phosphate, and the like;phosphonic acids such as diphenyl phosphonic acid, dioctyl phosphonicacid, dibutyl phosphonic acid, and the like; phosphonic acid esters suchas diethyl phenylphosphonate, and the like; phosphines such astriphenylphosphine, bis(diphenylphosphino)ethane, and the like; boricacids such as boric acid, phenylboric acid, and the like; aromaticsulfonic acid salts such as tetarabutylphosphoniumdodecylbenzensulfonate salt, and the like; organic halides such aschloride stearate, benzoyl chloride, chloride p-toluenesulfonate, andthe like; alkylsulfonic acids such as dimethylsulfonic acid, and thelike; organic halides such as benzyl chloride, and the like. Thesedeactivators are frequently used at 0.01 to 50 mol, preferably 0.3 to 20mol, with respect to the catalyst. After the catalyst has beendeactivated, there may be a step of removing low boiling point compoundsfrom the polymer by distillation. The distillation is preferablyperformed at reduced pressure, e.g. at a pressure of 0.1 to 1 mmHg at atemperature of 200 to 350° C. For this step, a horizontal deviceincluding a stirring blade having a high surface renewal capability suchas a paddle blade, a lattice blade, an eye glass-type blade or the like,or a thin film evaporator is preferably used.

It is desirable that the thermoplastic resin such as a polycarbonateresin has a very small amount of foreign objects. Therefore, the moltenproduct is preferably filtered to remove solids from the melt. The meshof the filter is preferably 5 μm or less, and more preferably 1 μm orless. It is preferred that the generated polymer is filtrated by apolymer filter. The mesh of the polymer filter is preferably 100 μm orless, and more preferably 30 μm or less. A step of sampling a resinpellet needs to be performed in a low dust environment, needless to say.The dust environment is preferably of class 6 or lower, and morepreferably of class 5 or lower.

The thermoplastic resin may be molded by any conventional moldingprocedure for producing optical elements. Suitable molding proceduresinclude but are not limited to injection molding, compression molding,casting, roll processing, extrusion molding, extension and the like.

While it is possible to mold the thermoplastic resin of the invention assuch, it is also possible to mold a resin composition, which contains atleast one thermoplastic resin of the invention and which furthercontains at least one additive and/or further resin.

Suitable additives include antioxidants, processing stabilizers,photostabilizers, polymerization metal deactivators, flame retardants,lubricants, antistatic agents, surfactants, antibacterial agents,releasing agents, ultraviolet absorbers, plasticizers, compatibilizers,and the like. Suitable further resins are e.g. another polycarbonateresin, polyester carbonate resin, polyester resin and the like, whichdoes not contain repeating units of the formula (I).

Examples of the antioxidant include but are not limited totriethyleneglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide,3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethylester,tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane,and the like.

The content of the antioxidant in the thermoplastic resin is preferably0.001 to 0.3 parts by weight with respect to 100 parts by weight of thethermoplastic resin.

Examples of the processing stabilizer include but are not limited tophosphorus-based processing stabilizers, sulfur-based processingstabilizers, and the like. Examples of the phosphorus-based processingstabilizer include phosphorous acid, phosphoric acid, phosphonous acid,phosphonic acid, esters thereof, and the like. Specific examples thereofinclude triphenylphosphite, tris(nonylphenyl)phosphite,tris(2,4-di-tert-butylphenyl)phosphite,tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite,trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite,dioctylmonophenylphosphite, diisopropylmonophenylphosphite,monobutyl-diphenylphosphite, monodecyldiphenylphosphite,monooctyldiphenylphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite,2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite,bis(nonylphenyl)pentaerythritoldiphosphite,bis(2,4-dicumylphenyl)pentaerythritoldiphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol-diphosphite,distearylpentaerythritoldiphosphite, tributylphosphate,triethylphosphate, trimethylphosphate, triphenylphosphate,diphenylmonoorthoxenylphosphate, dibutylphosphate, dioctylphosphate,diisopropylphosphate, dimethyl benzenephosphonate, diethylbenzenephosphonate, dipropyl benzenephosphonate,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphonite,tetrakis(2,4-di-t-butylphenyl)-4,3′-biphenylenediphosphonite,tetrakis(2,4-di-t-butylphenyl)-3,3′-biphenylenediphosphonite,bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite,bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and the like.The content of the phosphorus-based processing stabilizer in thethermoplastic resin composition is preferably 0.001 to 0.2 parts byweight with respect to 100 parts by weight of the thermoplastic resin.

Examples of the sulfur-based processing stabilizer include but are notlimited to pentaerythritol-tetrakis(3-laurylthiopropionate),pentaerythritol-tetrakis(3-myristylthiopropionate),pentaerythritol-tetrakis(3-stearylthiopropionate),dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate,distearyl-3,3′-thiodipropionate, and the like. The content of thesulfur-based processing stabilizer in the thermoplastic resincomposition is preferably 0.001 to 0.2 parts by weight with respect to100 parts by weight of the thermoplastic resin.

Preferred releasing agents contain at least 90% by weight of an ester ofan alcohol and a fatty acid. Specific examples of the ester of analcohol and a fatty acid include an ester of a monovalent alcohol and afatty acid, and a partial ester or a total ester of a polyvalent alcoholand a fatty acid. Preferred examples of the above-described ester of analcohol and a fatty acid include the esters of a monovalent alcoholhaving a carbon number of 1 to 20 and a saturated fatty acid having acarbon number of 10 to 30. Preferred examples of partial or total estersof a polyvalent alcohol and a fatty acid include the partial or totalester of a polyvalent alcohol having a carbon number of 2 to 25 and asaturated fatty acid having a carbon number of 10 to 30. Specificexamples of the ester of a monovalent alcohol and a fatty acid includestearyl stearate, palmityl palmitate, butyl stearate, methyl laurate,isopropyl palmitate, and the like. Specific examples of the partial ortotal ester of a polyvalent alcohol and a fatty acid includemonoglyceride stearate, monoglyceride stearate, diglyceride stearate,triglyceride stearate, monosorbitate stearate, monoglyceride behenate,monoglyceride caprylate, monoglyceride laurate, pentaerythritolmonostearate, pentaerythritol tetrastearate, pentaerythritoltetrapelargonate, propyleneglycol monostearate, biphenyl biphenate,sorbitan monostearate, 2-ethylhexylstearate, total or partial esters ofdipentaerythritol such as dipentaerythritol hexastearate and the like,etc. The content of the releasing agent in the resin composition ispreferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6parts by weight, and still more preferably 0.02 to 0.5 parts by weight,with respect to 100 parts by weight of the thermoplastic resin.

Preferred ultraviolet absorbers are selected from the group consistingof benzotriazole-based ultraviolet absorbers, benzophenone-basedultraviolet absorbers, triazine-based ultraviolet absorbers, cycliciminoester-based ultraviolet absorbers, and cyanoacrylate-basedultraviolet absorbers. Namely, the following ultraviolet absorbers maybe used independently or in a combination of two or more.

Examples of benzotriazole-based ultraviolet absorbers include2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazole-2-yl)phenol)],2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole,2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,2-(2-hydroxy-5-tert-butylphenyl)benzotriazole,2-(2-hydroxy-4-octoxyphenyl)benzotriazole,2,2′-methylenebis(4-cumyl-6-benzotriazolephenyl),2,2′-p-phenylenebis(1,3-benzoxazine-4-one),2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole,and the like.

Examples of benzophenone-based ultraviolet absorbers include2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone,2-hydroxy-4-methoxy-5-sulfoxybenzophenone,2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate,2,2′-dihydroxy-4-methoxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,2-hydroxy-4-n-dodecyloxybenzophenone,2-hydroxy-4-methoxy-2′-carboxybenzophenone, and the like.

Examples of triazine-based ultraviolet absorbers include2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-([(hexyl)oxy]-phenol,2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-([(octyl)oxy]-phenol,and the like.

Examples of cyclic iminoester-based ultraviolet absorbers include2,2′-bis(3,1-benzoxazine-4-one),2,2′-p-phenylenebis(3,1-benzoxazine-4-one),2,2′-m-phenylenebis(3,1-benzoxazine-4-one),2,2′-(4,4′diphenylene)bis(3,1-benzoxazine-4-one),2,2′-(2,6-naphthalene)bis(3,1-benzoxazine-4-one),2,2′-(1,5-naphthalene)bis(3,1-benzoxazine-4-one),2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one),2,2′-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one),2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one), and the like.

Examples of cyanoacrylate-based ultraviolet absorbers include1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane,1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.

The content of the ultraviolet absorber in the resin composition ispreferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0parts by weight, and still more preferably 0.05 to 0.8 parts by weight,with respect to 100 parts by weight of the thermoplastic resin. Theultraviolet absorber contained in such a range of content in accordancewith the use may provide a sufficient climate resistance to thethermoplastic resin.

As mentioned above, the thermoplastic polymer resins, in particular thepolycarbonate resins, comprising repeating units of formulae (II),(IIa), (IIa′), (IIb), (IIc), (IId), (IIe) and (IIf), respectively, asdescribed herein, provide high transparency and high refractive index tothermoplastic resins, which therefore are suitable for preparing opticaldevices, where high transparency and high refractive index is required.More precisely, the thermoplastic polycarbonates having structural unitsof formulae (II), (Ia), (Ia′), (IIb), (IIc), (IId), (IIe) and (IIf),respectively, are characterized by having a high refractive index, whichis preferably at least 1.660, more preferably at least 1.680, inparticular at least 1.690.

The contribution of the monomer of the formulae (I), (Ia), (Ia′), (Ib),(Ic), (Id), (Ie) and (If), respectively, to the refractive index of thethermoplastic resin, in particular a polycarbonate resin, will dependfrom the refractive index of said monomer and the relative amount ofsaid monomer in the thermoplastic resin. In general, a higher refractiveindex of the monomer contained in the thermoplastic resin will result ina higher refractive index of the resulting thermoplastic resin. Apartfrom that, the refractive index of a thermoplastic resin comprisingstructural units of the formula (II) can be calculated from therefractive indices of the monomers used for preparing the thermoplasticresin, either from the refractive index of the monomers or ab initio,e.g. by using the computer software ACD/ChemSketch 2012 (AdvancedChemistry Development, Inc.).

In the following table B the calculated refractive indices for somehomopolycarbonates consisting of structural units of the formulae (Ia′)and (ill-1) are given:

TABLE B # R^(x1) R^(x2) Ar n_(D) (calc.) 1 H H phenyl 1.68 2 H H1-naphthyl 1.71 3 H H 2-naphthyl 1.71 4 H H 9-phenanthryl 1.73 5 H H4-phenylphenyl 1.68 6 H H 3-phenylphenyl 1.68 7 H H 4-phenoxyphenyl 1.688 H H 9H-fluoren-2-yl 1.71 9 H H 1,2-dihydroacenaphthylen-5-yl 1.73 10 HH dibenzofuran-2-yl 1.73 11 H H dibenzofuran-4-yl 1.73 12 H Hdibenzothienyl-2-yl 1.74 13 H H dibenzothienyl-4-yl 1.74 14 H H4-quinolinyl 1.72 15 H H 2-quinolinyl 1.72 16 H H 3-quinolinyl 1.72 17 HH 1-isoquinolinyl 1.72 18 H H 4-isoquinolinyl 1.72 19 H H 1H-indol-3-yl1.70 20 H H 1H-pyrrol-2-yl 1.70 21 H H 1H-pyrrol-3-yl 1.70 22 H H2-pyridyl 1.69 23 H H 3-pyridyl 1.69 24 H H 4-pyridyl 1.69 25 H H5-pyrimidinyl 1.69 26 H H 2-cyanophenyl 1.76 27 H H 3-cyanophenyl 1.7628 H H 4-cyanophenyl 1.76 29 H H 4-cyano-1-naphthyl 1.79 30 H H5-cyano-1-naphthyl 1.79 31 H H 4-cyano-2-naphthyl 1.79 32 H H6-cyano-2-naphthyl 1.79

In case of thermoplastic copolymer resins, the refractive index of thethermoplastic resin, in particular a polycarbonate resin, can becalculated from the refractive indices of the homopolymers of therespective monomers, which form the copolymer resin, by the following socalled “Fox equation”:1/n _(D) =x ₁ /n _(D1) +x ₂ /n _(D2) + . . . x _(n) /n _(Dn),where n_(D) is the refractive index of the copolymer, x₁, x₂, . . .x_(n) are the mass fractions of the monomers 1, 2, . . . n in thecopolymer and n_(D1), n_(D2), . . . n_(Dn) are the refractive indices ofthe homopolymers synthesized from only one of the monomers 1, 2, . . . nat a time.

In case of polycarbonates, x₁, x₂, . . . x_(n) are the mass fractions ofthe OH monomers 1, 2, . . . n, based on the total amount of OH monomer.It is apparent that a higher refractive index of a homopolymer willresult in a higher refractive index of the copolymer.

The refractive indices of the thermoplastic resins can be determineddirectly or indirectly. For direct determination, the refractive indicesno of the thermoplastic resins are measured at wavelength of 589 nm inaccordance with the protocol JIS-K-7142 using an Abbe refractometer andapplying a 0.1 mm film of the thermoplastic resin. In case of therefractive indices of the homopolycarbonates of the compounds of formula(I), the refractive indices can also be determined indirectly. For this,a co-polycarbonate of the respective monomer of formula (I) with9,9-bis(4-(2-hydroxyethoxy)phenyl)-fluorene and diphenyl carbonate isprepared according to the protocol of example 1 in column 48 of U.S.Pat. No. 9,360,593 and the refractive indices no of the co-polycarbonateis measured at wavelength of 589 nm in accordance with the protocolJIS-K-7142 using an Abbe refractometer and applying a 0.1 mm film of theco-polycarbonate. From the thus measured refractive indices no, therefractive index of the homopolycarbonate of the respective monomer canbe calculated by applying the Fox equation and the known refractiveindex of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n_(D)(589nm)=1.639).

As mentioned before, compounds of formula (I), which do not bearcolor-imparting radicals, such as some of the radicals Ar, R and R′, canalso be obtained in a purity, which provides for a low yellowness indexY.I., as determined in accordance with ASTM E313, which may also beimportant for the use in the preparation of optical resins.

More precisely, the yellowness index Y.I., as determined in accordancewith ASTM E313, of the compounds of formula (I) preferably does notexceed 200, more preferably 100, even more preferably 50, in particular20 or 10.

Another aspect of the present invention relates to an optical devicemade of a thermoplastic resin as defined above, where the thermoplasticresin comprising a structural unit represented by the formula (II) andoptionally of formula (V). As regards to the preferred meanings andpreferred embodiments of the structural units of the formulae (II) and(V), reference is made to the statements given above.

An optical device made of an optical resin comprising the repeatingunits of the formula (II) and optionally repeating units of the formula(V) as defined herein are usually optical molded articles such asoptical lenses, for example car head lamp lenses, Fresnel lenses, fθlenses for laser printers, camera lenses, lenses for glasses andprojection lenses for rear projection TV's, CD-ROM pick-up lenses, butalso optical disks, optical elements for image display media, opticalfilms, film substrates, optical filters or prisms, liquid crystalpanels, optical cards, optical sheets, optical fibers, opticalconnectors, eposition plastic reflective mirrors, and the like. It isalso useful for producing a transparent conductive substrate usable foran optical device suitable as a structural member or a functional memberof a transparent conductive substrate for a liquid crystal display, anorganic EL display, a solar cell and the like.

The optical lens produced from the thermoplastic resin according to thepresent invention has a high refractive index and a low Abbe number, andis highly moisture and heat resistant. Therefore, the optical lens canbe used in the field in which a costly glass lens having a highrefractive index is conventionally used, such as for a telescope,binoculars, a TV projector and the like. It is preferred that theoptical lens is used in the form of an aspherical lens. Merely oneaspherical lens may make the spherical aberration substantially zero.Therefore, it is not necessary to use a plurality of spherical lenses toremove the spherical aberration. Thereby the weight and the productioncost of a device including the spherical aberration is decreased. Anaspherical lens is useful especially as a camera lens among varioustypes of optical lenses. The present invention easily provides anaspherical lens having a high refractive index and a low level ofbirefringence, which is technologically difficult to produce byprocessing glass.

An optical lens of the present invention may be formed, for example, byinjection molding, compression molding, injection compression molding orcasting the resin comprising the repeating units of the formula (II) andoptionally repeating units of the formula (V) as defined herein.

The optical lens of the present invention is characterized by a smalloptical distortion. An optical lens comprising a conventional opticalresin has a large optical distortion. Although it is not impossible toreduce the value of an optical distortion by molding conditions, thecondition widths are very small, thereby making molding extremelydifficult. Since the resin having repeating units of the formula (II)and optionally repeating units of the formula (V) as defined herein hasan extremely small optical distortion caused by the orientation of theresin and a small molding distortion, an excellent optical element canbe obtained without setting molding conditions strictly.

To manufacture the optical lens of the present invention by injectionmolding, it is preferred that the lens should be molded at a cylindertemperature of 260° C. to 320° C. and a mold temperature of 100° C. to140° C.

The optical lens of the present invention is advantageously used as anaspherical lens as required. Since spherical aberration can besubstantially nullified with a single aspherical lens, sphericalaberration does not need to be removed with a combination of sphericallenses, thereby making it possible to reduce the weight and theproduction cost. Therefore, out of optical lenses, the aspherical lensis particularly useful as a camera lens.

Since resins having repeating units of the formula (II) and optionallyrepeating units of the formula (V) as defined herein have a highmoldability, they are particularly useful as the material of an opticallens which is thin and small in size and has a complex shape. As a lenssize, the thickness of the center part of the lens is 0.05 to 3.0 mm,preferably 0.05 to 2.0 mm, more preferably 0.1 to 2.0 mm. The diameterof the lens is 1.0 to 20.0 mm, preferably 1.0 to 10.0 mm, morepreferably 3.0 to 10.0 mm. It is preferably a meniscus lens which isconvex on one side and concave on the other side.

The surface of the optical lens of the present invention may have acoating layer such as an antireflection layer or a hard coat layer asrequired. The antireflection layer may be a single layer or amulti-layer and composed of an organic material or inorganic materialbut preferably an inorganic material. Examples of the inorganic materialinclude oxides and fluorides such as silicon oxide, aluminum oxide,zirconium oxide, titanium oxide, cerium oxide, magnesium oxide andmagnesium fluoride.

The optical lens of the present invention may be formed by an arbitrarymethod such as metal molding, cutting, polishing, laser machining,discharge machining or edging. Metal molding is preferred.

An optical film produced by the use of the thermoplastic resin accordingto the present invention is high in transparency and heat resistance,and therefore is preferably usable for a liquid crystal substrate film,an optical memory card or the like. In order to avoid foreign objectsfrom being incorporated into the optical film as much as possible, themolding needs to be performed in a low dust environment, needless tosay. The dust environment is preferably of class 6 or lower, and morepreferably of class 5 or lower.

The following examples serve as further illustration of the invention.

I. Abbreviations

-   DCM: dichloromethane-   MEK: 2-butanone-   MeOH: methanol-   EtOH: ethanol-   MTBE: methyl tert-butyl ether-   RT: room temperature-   THF: tetrahydrofurane-   TLC: thin layer chromatography-   BPEF: 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene-   BNE: 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene-   DPC: Diphenyl carbonate

II. Preparation of the Compounds of Formula (I) II.1 Analytics

¹H-NMR spectra were determined at 23° C. using a 400 MHzNMR-spectrometer Avance III 400 HD from Bruker BioSpin GmbH. If notstated otherwise the solvent was CDCl₃

IR spectra were recorded by ATR FT-IR, using a Shimadzu FTIR-8400Sspectrometer (45 no. of scans, resolution 4 cm⁻¹; apodization:Happ-Genzel).

Melting points of the compounds were determined by Buchi Melting PointB-545.

UPLC (Ultra Performance Liquid Chromatography) analyses were carried outusing the following system and conditions:

Waters Acquity UPLC H-Class Systems; column: Acquity UPLC BEH C18, 1.7μm, 2×100 mm; column temperature: 40° C., gradient: acetonitrile/water:with acetonitrile at 0 min 50%, at 4 min 100%; at 5.8 min 100%; at 6.0min 50%; at 8.0 min 50%); injection volume: 0.4 μl; run time: 8 min;detection at 210 nm.

The yellowness index YI of the compounds of formula (I) can bedetermined by analogy to ASTN E313 using the following protocol: 1 g ofthe compound of formula (I) is dissolved in 19 g of a mixture ofMEK/water 95:5 (v/v). The solution is transferred into a 50 mm cuvetteand transmission is determined in the range 300-800 nm by a ShimadzuUV-Visible spectrophotometer UV-1650PC. A mixture of MEK/water 95:5(v/v) is used as a reference. From the spectra the yellowness index canbe calculated by using the Software “RCA-software UV2DAT” in accordancewith ASTM E308 (Standard practice for computing the colors of objects byusing the CIE System) und ASTM E 313 (Standard practice for calculatingyellowness and whiteness indices from instrumentally measured colorcoordinates).

The haze can be determined by measuring the transmission at 860 nm of a5% solution of the respective compound of formula (I) in a mixture ofMEK/water 95:5 (v/v) by a standard nephelometer.

II.2 Preparation Examples Example 1: Preparation of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-phenyl-methyl]-2-naphthyl]oxy]ethanol,(compound of formula (Ia′.1) 1.1:1-[[2-Hydroxy-1-naphthyl]-phenyl-methyl]-2-hydroxy-naphthalene (compoundof formula (VI) with R¹ and R² being hydrogen, Ar being phenyl and X¹,X², X³ and X⁴ being CH)

288.34 g (2 mol) of 2-naphthol were dissolved in 600 g (ca. 763 mL) ofisopropanol at RT. To this homogeneous solution 111.43 g (ca. 106.1 mL,1.05 mol) of benzaldehyde and 19.22 g (12.987 mL, 200 mmol) ofmethanesulfonic acid were added at RT. The initially homogeneousreaction mixture was stirred for at least 1.5 days at RT until a thickslurry was formed. The reaction was controlled via TLC (mobile phase:MeOH/water 7:3 (v/v)). Precipitated solid was filtered off, washedsubsequently with 40 g of isopropanol, and then with 50 g of pentane andthe solid was dried in vacuo at max. 30° C. under reduced pressure (180mbar). The first crop of the desired product was 161.69 g (ca. 43%). Themother liquor was concentrated using a rotary evaporator (at max. 40°C.) and stirred several hours at RT until a thick slurry was againformed. The precipitated solid was filtered off, washed with 20 g ofisopropanol, then with 25 g of pentane, and was finally dried in vacuoat max. 30° C. and 5 mbar. The second crop of the desired product was143.76 g (ca. 38.2%). Finally using the same procedure described above,additionally ca. 57.36 g (ca. 15.2%) as a third crop of the titlecompound was isolated, affording the title compound in a total yield of362.81 g (ca. 96.38%) as white crystalline powder, which was subjectedto the next step without additional purification.

m.p.=209-210° C.

1.2:2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-phenyl-methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.1)

A 1 L-three-neck round-bottom flask with reflux-condenser was purgedwith argon or nitrogen and charged with 50 g (132.82 mmol) of1-[[2-hydroxy-1-naphthyl]-phenyl-methyl]-2-hydroxy-naphthalene, whichwas then suspended in 270 mL (ca. 234 g) of toluene. Afterwards 35.1 g(398.5 mmol) of ethylene carbonate and 5.51 g (39.87 mmol) of potassiumcarbonate were added to the suspension and the reaction mixture wasstirred for 6-10 hours under reflux. The reaction was controlled via TLC(mobile phase: MeOH/water 7:3 (v/v)). After TLC analysis indicatedcompletion of the conversion, the reaction mixture was cooled to 70° C.,and 65 mL water were then slowly added to the mixture. Followingcompletion of the gas evolution and phase separation, the organic phasewas washed twice with 65 mL of 10% aqueous solution of sodium hydroxide,each, and twice or more with water until the aqueous wash solution isneutral (pH 7). The organic phase was then concentrated with a rotaryevaporator until an almost oily product was formed, 400-500 g of MTBEwere added and the crude product allowed to crystallize at RT. Theobtained crystalline solid was filtered off, washed with MTBE and driedto afford 29.4 g of the title compound (yield: 47.7%). Afterconcentration of the mother liquor additionally 15.54 g (ca. 25.2%) ofthe title compound were isolated. Total yield of the crude2,2′-[(phenylmethylene)bis(1,2-naphthyleneoxy)]diethanol was 44.94 g(ca. 72.8%). 43.8 g of the crude product were dissolved in 650 g of THEand the obtained homogeneous solution was treated with 4.5 g ofactivated charcoal at 50° C., filtered through Celite® and the solventwas completely removed with a rotary evaporator. Finally the titlecompound was purified by crystallization from MTBE to give 42.99 g ofthe pure title compound as colorless crystals with chemical purity of97.8%. After recrystallization of the title compound from MEK a chemicalpurity of >99% (UPLC) was achieved.

m.p.: 162.8-163.8° C.;

¹H NMR (400 MHz, CDCl₃): δ=2.51 (br s, 2H), 3.28 (ddd, J=12.54, 5.92,2.66 Hz, 2H), 3.31 (ddd, J=12.54, 5.92, 2.66 Hz, 2H), 3.68 (ddd, J=9.78,5.87, 2.57 Hz, 2H), 3.78 (ddd, J=9.78, 5.87, 2.57 Hz, 2H), 7.04 (s, 1H),7.35-7.58 (m, 12H), 7.93-8.10 (m, 5H) ppm;

IR [cm⁻¹]: 817.85 (71.0); 850.64 (78.7); 879.57 (72.8); 904.64 (76.4);960.58 (76.8); 976.01 (81.1); 1031.95 (65.4); 1047.38 (62.0); 1062.81(58.5); 1095.6 (60.6); 1145.75 (75.7); 1186.26 (82.3); 1215.19 (65.8);1240.27 (62.1); 1261.49 (58.6); 1300.07 (82.7); 1317.43 (76.8); 1344.43(81.5); 1369.5 (81.5); 1396.51 (86.9); 1411.94 (83.5); 1429.3 (77.3);1450.52 (76.8); 1465.95 (77.6); 1491.02 (78.8); 1510.31 (69.7); 1597.11(70.9); 1622.19 (78.5); 2868.24 (86.5); 2916.47 (87.9); 2928.04 (87.4);3182.65 (87.9); 3282.95 (86.0); 3360.11 (86.5); 3458.48 (87.4) cm⁻¹.

Example 2: Preparation of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-(1-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.2) 2.1:1-[[2-Hydroxy-1-naphthyl]-(1-naphthyl)methyl]-2-hydroxy-naphthalene(compound of formula (VI) with R¹ and R² being hydrogen, Ar being1-naphthyl and X¹, X², X³ and X⁴ being CH)

57.67 g (400 mmol) of 2-naphthol were dissolved in 560 mL (ca. 744.8 g)of DCM and then 35.35 g (215 mmol) of 1-naphthaldehyde and 3.84 g (40mmol, 10 mol-%) of methanesulfonic acid were added at RT. The reactionmixture was stirred at RT until TLC analysis (mobile phase: MeOH/water8:2 (v/v)) indicated complete consumption of 2-naphthol. The reactionmixture was quenched by neutralization with saturated aqueous solutionof sodium carbonate (50-60 mL). After phase separation the organic phasewas washed with water (2×100 mL) and the collected aqueous extracts wereextracted with DCM (3×50 mL). Finally, DCM is completely evaporated fromthe collected organic phases using a rotary evaporator and the crudeproduct was taken up in TBME (350 mL). The obtained suspension wasstirred for 1 hour at RT. Finally, the solid was filtered off, washedwith TBME (3×20 g) and dried, yielding 80.7 g (ca. 94.6%) of the titlecompound as an off-white crystalline solid with a chemical purity of99.26% (UPLC).

m.p.: 201.6° C.

2.2:2-[[1-[[2-(2-Hydroxyethoxy)-1-naphthyl]-(1-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.2)

A 2 L-three-neck round-bottom flask with reflux-condenser was purgedwith argon or nitrogen and charged with 200.46 g (470 mmol) of1-[[2-Hydroxy-1-naphthyl]-(1-naphthyl)methyl]-2-hydroxy-naphthalene,which was then suspended in 940 mL (ca. 815 g) of toluene. Afterwards124.17 g (1.41 mol) of ethylene carbonate and 19.5 g (141 mmol) ofpotassium carbonate were added to the suspension and the reactionmixture was stirred for 6-10 hours under reflux. The reaction wascontrolled via TLC (mobile phase: MeOH/water 8:2 (v/v)). During thereaction a solid precipitated. After TLC analysis indicated completeconversion, the reaction mixture was cooled to 70° C. and 65 mL of waterwere then slowly added to the mixture. After completion of the gasevolution the solid was filtered off, washed with toluene (2×100 mL) andwith water (3×100 mL). The solid was the suspended in MEK and water wasremoved via distillation of a MEK/water azeotrope. Finally, the productwas filtered off, washed with MEK to obtain 124.68 g (ca. 55.2%) of thetitle compound as a white solid. After purification via slurry wash inMEK at 60° C., filtration and drying the title compound was obtained ina yield of 118.15 g (ca. 52.3%) and a chemical purity of 96.48% (UPLC).

m.p.: 259.4-259.8° C.;

¹H NMR (400 MHz, DMSO-d₆): δ=2.77-3.19 (m, 4H), 3.24-3.80 (m, 4H), 4.31(br s, 1H), 4.50 (br s, 1H), 6.98 (s, 1H), 7.16-8.16 (m, 19H) ppm;

IR [cm⁻¹]: 812.06 (51.0); 856.42 (69.5); 893.07 (73.7); 929.72 (85.9);958.65 (77.2); 1010.73 (76.8); 1026.16 (63.2); 1041.6 (61.9); 1060.88(58.2); 1072.46 (58.9); 1091.75 (70.2); 1143.83 (74.3); 1186.26 (83.5);1234.48 (62.4); 1259.56 (61.3); 1269.2 (59.1); 1336.71 (75.2); 1373.36(79.4); 1394.58 (80.2); 1429.3 (78.3); 1448.59 (76.5); 1469.81 (82.3);1506.46 (70.0); 1597.11 (68.6); 1620.26 (76.6); 2868.24 (87.7); 2935.76(85.9); 3049.56 (87.8); 3360.11 (84.3) cm⁻¹.

Example 3: Preparation of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-(2-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.3) 3.1:1-[[2-Hydroxy-1-naphthyl]-(2-naphthyl)methyl]-2-hydroxy-naphthalene(compound of formula (VI) with R¹ and R² being hydrogen, Ar being2-naphthyl and X¹, X², X³ and X⁴ being CH)

72.085 g (500 mmol) of 2-naphthol were dissolved in 150 g (ca. 191 mL)of isopropanol at RT. To this homogeneous solution 40,639 g (255 mol) of2-naphthaldehyde and 4.81 g (50 mmol) of methanesulfonic acid were addedat RT. The initially homogeneous reaction mixture was stirred for 24hours at RT until a thick slurry was formed. The reaction was controlledvia TLC (mobile phase: MeOH/water 2:1 (v/v)). Precipitated solid wasfiltered off, washed subsequently with isopropanol (3×20 mL) and pentane(2×50 mL) and the solid was then dried in vacuo at max. 30° C. and 5mbar. The thus obtained first crop of the desired product was 27.0 g(ca. 25.3%) with a chemical purity of >96% (UPLC). The mother liquor wasconcentrated using a rotary evaporator (at max. 40° C.) and then stirredseveral hours at RT until a thick slurry was again formed. Theprecipitated solid was filtered off, washed with 20 g of isopropanol,then with 25 g of pentane, and was finally dried in vacuo at max. 30° C.and 180 mbar. The thus obtained second crop of the title compound was70.0 g (ca. 65.6%) with purity of >92% (UPLC). The title compound wasobtained as white crystalline powder in a total yield of ca. 97.0 g (ca.90.9%) and subjected for the next step without further purification.

m.p.: 177-179° C.

3.2:2-[[1-[[2-(2-Hydroxyethoxy)-1-naphthyl]-(2-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.3)

A 2 L-three-neck round-bottom flask with reflux-condenser was purgedwith argon or nitrogen and charged with 127.95 g (300 mmol) of1-[[2-hydroxy-1-naphthyl]-(2-naphthyl)methyl]-2-hydroxy-naphthalene,which was then suspended in 600 mL (ca. 520 g) of toluene. Afterwards79.3 g (900 mmol) of ethylene carbonate and 12.11 g (90 mmol) ofpotassium carbonate were added to the suspension and the reactionmixture was stirred for 6-10 hours under reflux. The reaction wascontrolled via TLC (mobile phase: MeOH/water 7:3 (v/v)). During thereaction a solid precipitated. After TLC analysis indicated completeconversion, the reaction mixture was cooled to 70° C. and 170 mL waterwere then slowly added to the mixture. After completion of the gasevolution and phase separation, the organic phase was washed twice with170 mL of a 10% aqueous solution of sodium hydroxide, each, and thentwice or more with water until the aqueous wash solution is neutral (pH7). The organic phase was then concentrated with a rotary evaporator andthe crude product was crystallized from toluene at 50° C. The obtainedcrystalline solid was filtered off, washed with cold toluene, then withpentane and dried to afford 101.64 g (ca. 65.84%) of the title compound.After concentration of the mother liquor additionally 11.94 g (ca.7.73%) of the title compound were isolated. Total yield of the crudetitle compound was 113.58 g (ca. 73.57%). After purification withactivated charcoal at 50° C., filtration through Celite® andrecrystallization from MEK or toluene, the title compound with a purityof 99.76% (UPLC) was obtained.

m.p.=164° C.;

¹H NMR (400 MHz, CDCl₃): δ=2.28 (br s, 2H), 2.93-3.03 (m, 1H), 3.10-3.26(m, 3H), 3.47-3.55 (m, 1H), 3.65-3.79 (m, 3H), 7.15-7.44 (m, 10H), 7.558(s, 1H), 7.60-7.91 (m, 9H) ppm;

IR [cm⁻¹]: 804.34 (50.8); 856.42 (64.0); 900.79 (70.2); 960.58 (77.3);1030.02 (61.8); 1062.81 (54.9); 1093.67 (66.8); 1124.54 (85.9); 1149.61(76.0); 1163.11 (81.0); 1207.48 (68.0); 1238.34 (62.8); 1259.56 (56.8);1292.35 (82.8); 1334.78 (75.9); 1352.14 (83.5); 1371.43 (79.3); 1410.01(83.1); 1429.3 (77.4); 1448.59 (76.0); 1469.81 (78.4); 1510.31 (69.9);1573.97 (87.5); 1597.11 (70.1); 1620.26 (76.4); 2872.1 (85.8); 2935.76(84.9); 3053.42 (87.0); 3383.26 (84.8); 3419.9 (85.0); 3564.57 (86.5)cm⁻¹.

III. Preparation of the Resins III.1 Analytics III.1.1 MeasurementMethod of Weight Average Molecular Weight (Mw) and Number AverageMolecular Weight (Mn)

The weight average molecular weight (Mw) was measured using theHLC-8320GPC device from Tosoh Corporation as a GPC device, theTSKguardcolumn SuperMPHZ-Mone as a guard column, and three TSKgelSuperMultiporeHZ-M(s) connected in series as analysis columns. Themeasurement conditions were as follows.

-   -   Solvent: HPLC grade chloroform    -   Injection Volume: 10 μL    -   Concentration of Sample: 0.2 w/v % HPLC grade chloroform        solution    -   Solvent flow velocity”: 0.35 ml/min    -   Measurement Temperature: 40° C.    -   Detecting Device: RI

The polystyrene converted weight average molecular weights (Mw) andnumber average molecular weights (Mn) are calculated using thepreviously prepared standard curve of polystyrene. Specifically, thestandard curve was prepared using a standard polystyrene of which themolecular weight was known (“PStQuick MP-M” from Tosoh Corporation whichhas molecular weight distribution value of 1). Further, a calibrationcurve was obtained by plotting the elution time and molecular weightvalue of each of the peaks based on the measured data of the standardpolystyrene, and conducting three-dimensional approximation. The valuesfor Mw and Mn are calculated based on the following calculationformulae.Mw=Σ(Wi×Mi)+Σ(Wi)Mn=Σ(Ni×Mi)+Σ(Wi)

In the calculation formula, “i” represents the “i”th dividing point,“Wi” represents the molecular weight (g) of the polymer at the “i”thdividing point, “Ni” represents the number of the molecules of thepolymer at the “i”th dividing point, and “Mi” represents the molecularmass at the “i”th dividing point. The molecular mass (M) represents thevalue of the molecular mass of polystyrene at the corresponding elutiontime in the calibration curve.

III.1.2 Refractive Index (n_(D))

The refractive index of a film having a thickness of 0.1 mm formed of apolycarbonate resin produced in an example was measured by use of anAbbe refractive index meter by a method of JIS-K-7142 at a wavelength of589 nm.

III.1.3 Abbe Number (v)

The refractive index of a film having a thickness of 0.1 mm formed of apolycarbonate resin produced in an example was measured by use of anAbbe refractive index meter at 23° C. at wavelengths of 486 nm, 589 nmand 656 nm. Then, the Abbe number was calculated by use of the followingequation:v=(n _(D)−1)/(n _(F) −n _(C))

-   -   n_(D): refractive index at a wavelength of 589 nm    -   n_(C): refractive index at a wavelength of 656 nm    -   n_(F): refractive index at a wavelength of 486 nm

III.1.4 Glass Transition Temperature (Tg)

The glass transition temperature was measured by differential scanningcalorimetry (DSC) according to JIS K 7121-1987. The measuring device wasa X-DSC7000 from Hitachi High-Technologies.

III.1.5 Measurement of b Value

The respective resin was dried at 120° C. for 4 hours in vacuum, andthen injection-molded by an injection molding device (FANUC ROBOSHOTα-S30iA) at a cylinder temperature of 270° C. and a mold temperature ofTg−10° C. to obtain a disc-shaped test plate piece having a diameter of50 mm and a thickness of 3 mm. This test plate piece was used to measurethe b value by a method according to JIS-K7105. When the b value issmaller, the plate is less yellowish and thus the hue is better. For themeasurement, a spectral color difference meter type SE2000 of NipponDenshoku Industries Co., Ltd. was used.

III.1.6 Total Light Transmittance (TLT)

A plate having a thickness of 3 mm was produced from the respectivepolycarbonate resin by the protocol described in section III.1.5 for themeasurement of the b value. The total light transmittance of measured byuse of SE2000 spectral color difference meter produced by NipponDenshoku Industries Co., Ltd. by a method of JIS-K-7361-1.

The total light transmittance of these plates were measured before a PCTtreatment and thereafter. The latter value is given in table C in columnTLT-PCT.

III.1.7 Amount of Vinyl Terminal Group

The amount of vinyl terminal groups was determined by ¹H-NMR measurementunder the following conditions.

-   -   Device: AVANZE III HD 500 MHz produced by Bruker    -   Flip angle: 30 degrees    -   Wait time: 1 second    -   Accumulate number of times: 500 times    -   Measurement temperature: room temperature (298K)    -   Concentration: 5 wt %    -   Solvent: Deuterated chloroform    -   Inner standard substance: tetramethylsilane (TMS) 0.05 wt %

III.1.8 Determination of Impurities in the Resin

Concentrations of phenol, diphenylcarbonate (DPC) and monomer in thepolycarbonate resin was measured according to the following protocol.

0.5 g of the resin sample was dissolved in 50 ml of tetrahydrofuran toobtain a resin solution. A calibration curve was created from a pureform of each of compounds as a preparation. 2 μL of sample solution wasquantitatively analyzed by LC-MS under the following measurementconditions. The detection limit under the measurement conditions is 0.01ppm.

-   -   Measurement device (LC part): Agilent Infinity 1260 LC System    -   Column: ZORBAX Eclipse XDB-18 and guard cartridge    -   Mobile phase:        -   Eluent A: 0.01 mol/L—aqueous solution of ammonium acetate        -   Eluent B: 0.01 mol/L—methanol solution of ammonium acetate        -   Eluent C: THE        -   Gradient program of the mobile phase:

As shown in Table 1, different mixtures of eluents A through C were usedas mobile phases. The mobile phases were caused to flow in the columnfor 30 minutes while the compositions of the mobile phases were switchedwhen the time (minutes) shown in Table 1 lapsed.

TABLE 1 Time Mobile Phase Composition (% by Volume) (min.) A B C 0 10 7515 10.0 9 67.5 23.5 10.1 0 25 75 30.0 0 25 75 Flow rate: 0.3 ml/min.Column temperature: 45° C. Detector: UV (225 nm) Measurement device (MSpart): Agilent 6120 single quad LCMS System Ionization source: ESIPolarity: Positive (DPC) and negative (PhOH) Fragmentor: 70 V Dry gas:10 L/min., 350° C. Nebulizer: 50 psi Capillary voltage: 3000 V(positive), 2500 V (negative) Ion measured

TABLE 2 Monomer Ion Type m/z PhOH [M − H]⁻ 93.1 DPC [M + NH₄]⁺ 232.1Amount of injected sample: 2 μL

III.1.9 Moldability of Resins

The moldability of the polycarbonate resins was evaluated preparingplates as described in protocol 3.1.5 and visually assessing the qualityof the plates according to the following grades A to D:

-   A: Molded piece had no void space and no wave was found on the    surface of the molded piece.-   B: Molded piece had void space while no wave was found on the    surface of the molded piece.-   C: Molded piece had no void space while waves were found on the    surface of the molded piece.-   D: Molded piece had void space while waves were found on the surface    of the molded piece.

III.2 Preparation Examples Example 4-1

7.70 g (0.016 mol) of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-phenyl-methyl]-2-naphthyl]oxy]ethanol(compound of the formula (Ia′.1)), 28.19 g (0.064 mol) of BPEF, 17.73 g(0.083 mol) of DPC and 32 μl (8.0×10⁻⁷ mol) of a 2.5×10⁻² mol/L aqueoussolution of sodium hydrogen carbonate were put into a 300 ml four-neckflask reactor in a nitrogen atmosphere. The mixture was heated to 190°C. to start the reaction. The reaction mixture was stirred at 190° C.for 60 minutes and then heated to 200° C. The reaction conditions weremaintained for further 20 minutes. Then, the pressure was adjusted to200 mmHg, and the reaction conditions were maintained for further 20minutes. At this point, phenol generated as a byproduct started todistill off. Then, the reaction mixture was heated to 230° C. and thereaction conditions were maintained for further 10 minutes. Then, thepressure was adjusted to 150 mmHg and the reaction conditions weremaintained for further 10 minutes. The reaction mixture was heated to240° C. while the pressure was adjusted to lower than or equal to 1mmHg. The reaction mixture was stirred for 30 minutes with maintainingthe temperature and pressure. After the reaction was completed, pressureequalization was achieved by introducing nitrogen into the reactor andthe generated polycarbonate was removed from the reactor and analyzed.The results are summarized in table C.

In the polycarbonate obtained in Example 4-1, the content of phenol was300 ppm while the content of diphenylcarbonate was 150 ppm.

Example 4-2

Substantially the same operation was performed as in example 4-1 exceptthat 19.20 g (0.0414 mol) of the compound of formula (Ia′.1) and 17.60 g(0.040 mol) of BPEF were used as dihydroxy compounds to obtain apolycarbonate resin.

Example 4-3

Substantially the same operation was performed as in example 4-1 exceptthat 8.30 g (0.0161 mol) of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-(1-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.2)) and 28.30 g (0.0645 mol) of BPEF were usedas dihydroxy compounds to obtain a polycarbonate resin.

Example 4-4

Substantially the same operation was performed as in example 4-1 exceptthat 21.30 g (0.0414 mol) of the compound of formula (Ia′.2) and 18.10 g(0.0413 mol) of BPEF were used as dihydroxy compounds to obtain apolycarbonate resin.

Example 4-5

Substantially the same operation was performed as in example 4-1 exceptthat 8.30 g (0.0161 mol) of2-[[1-[[2-(2-hydroxyethoxy)-1-naphthyl]-(2-naphthyl)methyl]-2-naphthyl]oxy]ethanol(compound of formula (Ia′.3)) and 28.30 g (0.0645 mol) of BPEF were usedas dihydroxy compounds to obtain a polycarbonate resin.

Example 4-6

Substantially the same operation was performed as in example 4-1 exceptthat 21.30 g (0.0414 mol) of the compound of formula (Ia′.3) and 18.10 g(0.0413 mol) of BPEF were used as dihydroxy compounds to obtain apolycarbonate resin.

Reference Example 5

Substantially the same operation was performed as in example 4-1 exceptthat 6.20 g (0.0166 mol) of BNE and 29.00 g (0.0661 mol) of BPEF wereused as dihydroxy compounds to obtain a polycarbonate resin.

Properties of the resins obtained in Examples 4-1 to 4-6 and ReferenceExample 5 are shown in Table C.

TABLE C Molar Ratio of Dihydroxy Compounds Compound Compound CompoundMolecular Weight Example (Ia′.1) (Ia′.2) (Ia′.3) BPEF BNE M_(W) Mn Mw/Mn4-1 20.0 0.0 0.0 80.0 0.0 68976 7751 8.899 4-2 50.8 0.0 0.0 49.2 0.051361 6928 7.414 4-3 0.0 20.0 0.0 80.0 0.0 16557 4452 3.719 4-4 0.0 50.10.0 49.9 0.0 12760 3780 3.376 4-5 0.0 0.0 20.0 80.0 0.0 50427 7655 6.5874-6 0.0 0.0 50.0 50.0 0.0 28329 11997 2.361 5¹⁾ 0.0 0.0 0.0 80.0 20.069076 6734 10.258 Tg Abbe TLT²⁾ b Mold- TLT-PCT³⁾ Ex. [° C.] n_(D) n_(C)n_(F) no. (v) [%] value ability [%] 4-1 146.9 1.6439 1.6359 1.6644 22.6089 4.0 A 89 4-2 149.8 1.6505 1.6447 1.6751 21.38 88 4.1 B 88 4-3 152.91.6498 1.6415 1.6711 21.97 89 4.0 A 89 4-4 165.8 1.6643 1.6469 1.679920.14 88 4.0 B 88 4-5 150.9 1.6482 1.6399 1.6694 22.02 89 4.0 A 89 4-6160.0 1.6603 1.6543 1.6869 20.25 88 4.0 B 88 5¹⁾ 139.4 1.6446 1.63441.6630 22.53 85 4.3 D 85 ¹⁾reference example 5; ²⁾total lighttransmittance of the finished resin; ³⁾total light transmittance of theresin after PCT test.

We claim:
 1. A thermoplastic resin comprising a structural unitrepresented by formula (II) below

where # represents a connection point to a neighboring structural unit;R¹, R² are hydrogen, a radical R^(a) or R¹ and R² together with thecarbon atoms to which they are bound may also form a fused benzene ring,which is unsubstituted or substituted by one radical R^(a), Y representsan alkylene group having 2, 3 or 4 carbon atoms, Ar is selected from thegroup consisting of mono- or polycyclic aryl having from 6 to 26 carbonatoms and mono- or polycyclic hetaryl having a total of 5 to 26 atoms,which are ring members, where 1, 2, 3 or 4 of these atoms are selectedfrom nitrogen, sulphur and oxygen, while the remainder of these atomsare carbon atoms, where mono- or polycyclic aryl and mono- or polycyclichetaryl are unsubstituted or carry one, two, three or four radicalsR^(Ar); X¹, X², X³, X⁴ are CH, C—R^(x) or N, provided that in each ringat most two of X¹, X², X³, X⁴ are N; R^(a) is selected from the groupconsisting of fluorine, cyclopropyl, cyclobutyl, CN, R, OR,CH_(n)R_(3-n), NR₂, C(O)R, C(O)NH₂, CH═CH₂, CH═CHR′, CH₂—CH═CH₂,CH₂—CH═CHR′, CH₂—C≡CH and CH₂—C≡CR′; R^(Ar) is selected from the groupconsisting of fluorine, cyclopropyl, cyclobutyl, CN, R, OR,CH_(n)R_(3-n), NR₂, C(O)R, C(O)NH₂, CH═CH₂, CH═CHR′, CH₂—CH═CH₂,CH₂—CH═CHR′, CH₂—C≡CH and CH₂—C≡CR′, wherein each R^(Ar) is identical ordifferent if more than one R^(Ar) is present on each ring; R^(x) isselected from the group consisting of halogen, cyclopropyl, cyclobutyl,CN, R, OR, CH_(n)R_(3-n), NR₂, C(O)R, CH═CH₂, CH═CHR′, CH₂—CH═CH₂,CH₂—CH═CHR′, CH₂—C≡CH and CH₂—C≡CR′, wherein each R^(x) is identical ordifferent if more than one R^(x) is present on each ring; R is selectedfrom methyl, mono- or polycyclic aryl having from 6 to 26 carbon atomsand mono- or polycyclic hetaryl having a total of 5 to 26 atoms, whichare ring members, where 1, 2, 3 or 4 of the ring atoms of hetaryl areselected from nitrogen and oxygen, while the remainder of these atomsare carbon atoms, where mono- or polycyclic aryl are unsubstituted orsubstituted by one, two, three or four identical or different radicalsR″; R′ is selected from methyl, mono- or polycyclic aryl having from 6to 26 carbon atoms and mono- or polycyclic hetaryl having a total of 5to 26 atoms, which are ring members, where 1, 2, 3 or 4 of the ringatoms of hetaryl are selected from nitrogen and oxygen, while theremainder of these atoms are carbon atoms, where mono- or polycyclicaryl are unsubstituted or substituted by one, two, three or fouridentical or different radicals R″; R″ is selected from fluorine,cyclopropyl, cyclobutyl, phenyl, CN, OCH₃, CH₃, N(CH₃)₂, C(O)CH₃,CH═CH₂, CH═CHCH₃, CH₂—CH═CH₂, CH₂—CH═CH—CH₃, CH₂—C≡CH and CH₂—C≡C—CH₃;and n is each 0, 1, 2 or 3; wherein the thermoplastic resin has arefractive index at 23° C. at a wavelength of 589 nm of 1.6439 orhigher.
 2. The thermoplastic resin of claim 1, where the structural unitis connected to one of the structures represented by formulae (III-1) to(III-5) below,

where # represents a connection point to a neighboring structural unit.3. The thermoplastic resin of claim 1, which is selected fromcopolycarbonate resins, copolyestercarbonate resins and copolyesterresins, where the thermoplastic resin in addition to structural unitsrepresented by formula (II) comprises a structural unit of the formula(V),#—O—R^(z)-A³-R^(z)—O-#-  (V) where # represents a connection point to aneighboring structural unit; A³ is a polycyclic radical bearing at leasttwo benzene rings, wherein the benzene rings may be connected by A′and/or directly fused to each other and/or fused by a non-benzenecarbocycle, where A³ is unsubstituted or substituted by one, two orthree radicals R^(aa), which are selected from the group consisting ofhalogen, C₁-C₆-alkyl, C₅-C₆-cycloalkyl and phenyl; A′ is selected fromthe group consisting of a single bond, O, C═O, S, SO₂, CH₂, CH—Ar″,CHAr″₂, CH(CH₃), C(CH₃)₂ and a radical of the formula (A″)

where Q′ represents a single bond, O, NH, C═O, CH₂ or CH═CH; andR^(10a), R^(10b) independently of each other are selected from the groupconsisting of hydrogen, fluorine, CN, R, OR, CH_(k)R_(3-k), NR₂, C(O)Rand C(O)NH₂, where k is 0, 1, 2 or 3; Ar″ is selected from the groupconsisting of mono- or polycyclic aryl having from 6 to 26 carbon atomsand mono- or polycyclic hetaryl having a total of 5 to 26 atoms, whichare ring members, where 1, 2, 3 or 4 of these atoms are selected fromnitrogen, sulphur and oxygen, while the remainder of these atoms arecarbon atoms, where Ar” is unsubstituted or substituted by one, two orthree radicals R^(ab), which are selected from the group consisting ofhalogen, phenyl and C₁-C₄-alkyl; R^(z) is a single bond, Alk¹ or O-Alk²-where O is bound to A³, and where Alk¹ is C₂-C₄-alkandiyl; and Alk² isC₂-C₄-alkandiyl.
 4. The thermoplastic resin of claim 3, where thestructural unit of the formula V is represented by one of the followingformulae V-1 to V-8:


5. An optical device made of a thermoplastic resin as defined inclaim
 1. 6. The optical device of claim 5, wherein the optical device isan optical lens or an optical film.